dude, i love that book. i have that and the previous edition. I second the recommendation. Note though that it's a HUGE book. I used that book to get a lifting start on programming for the .NET framework. (Guys, however you slice it, C# and VB.NET all just compile to MSIL anyway)
From there, branch out into other books (if you're like me, and you have to read alot of material before you *get it*) .. for ASP.NET i got ASP.NET 3.5 Unleashed and when I dove into XNA i got Microsoft XNA Unleashed and Professional XNA Game Programming.
From there, it's been using the MSDN forums and google to dig up more topics on how to do this or that. Get really familiar with using MSDN online because it's your bestest friend ever when you want to figure something out.
