Official Nvidia drivers will not allow a physX card to be used in the presence of an ATI card. Depending on what your operating system is, you may be able to apply a workaround.
My personal, but very limited experience with ati + physx, is that the physX card becomes the bottleneck, and by using older cards, I was crippled with physX enabled. Since i was looking at a budget way to accomplish it, I wasn't willing to shell for a faster card just to run PhysX on the very few titles that actual utilize it in that way.