jpar, forgive my giving an opinion. But best you learn to walk before running. I think you will be a lot more benefited by learning Mental Ray and using shaders and textures before thinking of Vray. Lights are very important, and you need to get your feet wet with them. Not that there is that big of difference in the usage of shaders and textures in Vray and Mental Ray. But a lot more training available for Mental Ray than Vray.

Just a thought!!