VB.NET and C# are both based on the .NET framework, they're Microsoft languages.
The overall framework is identical, i.e. the class hierarchy is the same. The only difference is in the syntax. C# reads a lot like C++.
You can get Visual C# Express 2005 for free from MS, just search in Google and it should come up with a download link.
There are loads of forums around with advice, tutorials etc.
www.codeproject.com is a very good resource as well as MSDN.
If you do want to do GUI stuff and want a career as a software developer then I would advise this route way above C++. There is very little demand for GUIs written in C++ and you will learn all you need from C#.