The education section and the XNA Forums are probably the best I've ever seen, so you should be good hanging around here and digging for resources :)
All programming languages share common features/concepts. Since the .NET platform is an evolution and friend to language like C, C++ and Java, you might want to study a few different languages at once. I can't say that GameDev's been the best resource. It's too generalized, in my opinion. When you want to get into the specifics and theory of certain techniques, you want to look elsewhere - Online tutorials and code snippets usually get the job done.
One thing you really want to do as a programmer is face conquer challenges you couldn't before. One thing I did that vastly expanded my programming knowledge was hang around forums just like these and look for posts I didn't understand. Whenever there was a topic that confused me, I researched it until I so good I could provide advice to others. In game development, we often see programming as an artistic canvas, and since there's so many different ways to paint the same picture, sometimes we don't do the type of research we should...