A question may arise as to why Dev was never drawn towards Amba despite her 15 year long pursuance. The answer lies in the stark contrast in the personalities of Vidhi and Amba.
The first thing that made Dev take notice of Vidhi was her honesty and simplicity, both of which are missing in Amba. Amba is neither simple nor honest, she is manipulative and plays with words to twist the situation under her control.
Dev himself being simple and truthful, values the same in others. And Vidhi is the epitome of simplicity. So, of course he would be drawn towards her. How could he ever be drawn towards anyone as manipulative as Amba, even if we ignore her obsession for a moment (obsession on Amba's part repulsed Dev even farther).
The next thing that made Dev in awe of Vidhi was her simple yet deep philosophy towards life, which affected him so much that he incorporated that philosophy in his decision-making like the "lohe ki kulhadi" story, "being trustful in relationship" advice for her mother, saving "paper" and limiting wastage in office. In contrast, Amba has no principle or philosophy that she lives by, her philosophy changes with situation because only end goal matters to her, she has no deep rooted philosophy or principle she goes by.
Vidhi's words, though simple, are straight from her heart and direct, not coated or filtered by anything motive-oriented and that's why they reach Dev's heart. Even simple words spoken by her have had a deep impact on Dev from the beginning, for example - "Iss suit mein toh aap chand se bhi dikh jaayein", "keeping change in wallet always", "treat vs party", all these made an impact on Dev because they were truthful and honest but not aimed at pleasing him. And Dev converted her words and advice into action. Vidhi's words touch Dev's heart because they are truthful and from her heart and these words impact his life like nothing else has in a long long time. Like Dev says, "wo badlaav jisse main zindagi bhar bachta aaya hun".
Another thing that drew Dev towards Vidhi was that being so naive, out-of-the-world inexperienced and simple-minded, she needed protection at many levels. And given Dev's history as a protecter of his family from an early age, he felt the need to protect her, to teach her world's ways. This added another layer to their relationship. This was never the case with Amba. He never felt the need to protect her because she never really needed his protection, she was self sufficient from the get go, she knew how to bend the world at her will.
All these things established an unsaid connection between Vidhi and Dev- one of trust, unsaid understanding, simplicity and honesty. This connection made him confide in her, like telling her the Balghar secret he says, "main nahin jaanta tumhe kyun bata raha hun", like after "Khaugali Treat" he said, "main yahan tumhaare saath aaya, bina soche bina samjhe, pata nahin kyun". May be on surface he doesn't know why but deep down her honesty and truthfulness had made an impression on him that she is trustworthy and he can share things with her without inhibition. Of course, all those years the shell that Dev had made around him, not letting anyone in, kept interfering for a while and initially he did doubt her for a few things, "that note of secrets", "gossip about him and Amba", but soon he realised that he is wrong and now he trusts Vidhi completely, so completely that even when her parents don't believe her, he does - like in the alcohol fiasco. He could never feel this connection with Amba because he never found her trustworthy due to her manipulative nature.
From the very beginning, the thing that drew Dev towards Vidhi and made a place for her in his heart were her out-of-the-world nativity and innocence as he kept telling her in awe many-a-times - "Kya ho tum Ms. Vidhi". All his life, he has dealt with worldly people (including Amba), but not someone as out of world as Vidhi. So, he is often taken aback by her unworldly simplicity. Her unpolluted naive approach towards the world showed him a new perspective at times, in his own words, "Kuch toh khaas hai tum mein". At his stature and position, he is surrounded by people who want to please him all the time, Amba included, although her motive is different than others. And thus, Vidhi is the much needed breath of fresh air in his life.
Quoting what Rochester said about Jane (another age-gap story from the novel Jane Eyre) - "a rare one, a gentle gracious stranger of the such good and bright qualities, which you have sought for twenty years, and never before encountered; and they are all fresh, healthy, without soil and without taint. Such society (company) revives, regenerates: you feel better days come back — higher wishes, purer feelings; you desire to recommence your life, and to spend what remains to you of days in a way more worthy of an immortal being.”
This is what Vidhi is to Dev, the one whose innocence and out-of-the-world freshness, turns his rugged existence burdened with thousands of responsibilities into a light, smooth and peaceful existence, that is worth living and enjoying, in his own words, "woh saathi har koi chahta hai jo sukoon de jaaye, woh chehra jisse dekhkar saari pareshaniya dur ho jaaye aur aap muskurane lage", and indeed we can see his relaxed and comforted side when she is around (of course before he knew she has feelings for him and he tried to restrain him around her). She is the one whose words makes him better man every day, in his own words, "pyar jo aapki kamiyan bhar de, jiska result log aapke actions mein dekh sakey", and indeed we can see the changes in him, clear as day. All these are things that Amba could never be for him, so he was never drawn towards her.
On a more philosophical note, a dialogue from the serial "Kuch Toh Log Kahenge" seems fit to answer this question at hand. There was similar situation there. Mallika (Amba's counterpart) asks Ashutosh (Dev's counterpart), "Why couldn't you ever love me, though I loved you all these years with all my heart". The answer Ashutosh (Dev's counterpart) gives sums it all. He says, "Two dried up rivers can never quench anyone's thirst, let alone each other's, they can never complete each other. We both are like that, so we can never give comfort to each other even if we come together".
Amba longs for Dev as if without him she has nothing in her life, like a dried up river in wait for water. But Dev is dried up too, from the life-long responsibilities, so much so that Dev loves his family but never confides in them, even his mother untill Vidhi makes him understand. How can they both ever fulfill each other.
Vidhi always lacked self-confidence but she was full of life from the beginning. Her interaction with her family, especially her sister and Balghar's kids (in front of whom she could be her true self without any fear), were so joyous and lively. Only in front of people who constantly criticised her, she became nervous and made blunders. Vidhi has that childish spark that brings out the child-like aspirations in Dev, for example in the Khaugali Treat where he says, "Tumne aaj mujhe zindagi bhar ka bachpan de diya". That day he breathed free again after so many years. Away from his responsibilities, he laughed freely again, and in his own words, "kitna maza kiya, khaya piya naacha".
Vidhi's innocence broke Dev's inhibition of maintaining a certain stature around people, like when he laughed whole-heartedly at with her innocent "pakka hisab of sorry and thank you". As remarked by his driver, it was after so long that Dev had a good open laugh. And he enjoyed pulling her leg about this on many occasions after that, "aur aajka hisab", "aaj thank you aur sorry ka hisab nahin karogi?"
One one hand her innocence makes him at ease around her and on the other hand, her fresh insights on life mesmerise him, in his own words, "itni si umar mein kabhi kabhi kitni gehri baat kar jaati ho." How can he be not drawn towards her, how can he not fall for her, after all she is all that was missing from his life for so long. And that is what happened, slowly Vidhi made an imprint in his heart without him knowing, she became a friend with whom he could share his heart, though because of his closed nature, he kept her at bay or at least tried to. And we all know with time, you never know when that imprint turns into love, which is what is happening with him now, leaving him confused.