Visual Studio .NET was developed by microsoft, so the learning curve for the GUI is easy if you have used other microsoft programs before. Also, I have been learning asp .net, vb .net and c# .net for the past 4-5 months and I must say that I allready have a reasonable knowledge of each language. The only language I have programmed in before these was vb6 and a little c/c++ so, I haven't had much experience. The learning is quick and fun. What languages are you using at the moment? Some good books are:

SAMS teach yourself vb .net in 24 days
SAMS teach yourself asp .net in 24 days

I have both books (I think it's 24 days lol, I forget) but yeah. Basically I read a little of those as well as do some research on the web. It seems hard starting off but it doesn't take long for you to get used to it.

Hope I helped,

Slade