Well, first, do you have VS.Net installed on your Pc or do you have frequent access to use VS.Net?, that's help.
The Wrox books for .Net are great, I found them easily to understand and great help... hence I am here. Please, tell me which language you are going to be use, I can recommend some books, sites for you. The MSDN, www.msdn.microsoft.com
is your reference, all in there but sometimes it hard to find what you're looking for. C# Help for C# language, http://www.csharphelp.com
, quite good for finding C# related problem. Here at wrox if you don't know just buzz us and someone will help you.
Also Pending on how much you have been programming before, .Net is fully object oriented programming, you need to know basic of OOP. Knowing VB6, VC++, or JAVA will make it easier. Any questions, give a buzz.