The short answer is no.

Texture coords and Poly coords are separate. It's even encouraged to move the UVs around a little bit when working on humans for example in areas where texture stretching appears (usually around the mouth). This will look odd in the UV editor but great when you render it and that's what counts. Someone more tech savvy might be able to answer this more indepth, but I wouldn't worry. Just relax your UVs so you can see what's going on when you paint it. Mike's book The Game Artists Guide To Maya explains all of this and much more and I can highly recommend it.