Well, all the Nvidia card would do is PhysX, so only games with PhysX support would see any benefit. Probably a good idea to go for an NVidia card in the 200 series as the cost:benefit ratio gets pretty silly when doing this with the 400 series cards.
There are pretty much 2 advantages to this setup:
1. You get to use PhysX while having an ATI card as your primary rendering card.
2. You get a card dedicated to rendering and another dedicated PhysX, this takes a LOT of load off the rendering card which can easily get bogged down trying to do both.
Disadvantages:
1. The setup isn't supported, NVidia is in fact against the setup completely and recently explicity disabled the ability to use this setup in their drivers.
2. You have to use some community developed hacks that modify your installed NVidia driver so it doesn't disable itself when detecting an ATI GPU.
3. Support for those hacks are best effort and made and maintained by people in their spare time, with NVidia actively working against them, so you take an expensive gamble on how long the setup will continue to work.