I am from a Visual Basic background myself and after already having a subscription I found http://www.learnvisualstudio.net to be very useful. I don't think you would have any problems learning both C# and C++ as C# was modeled mostly on C++.
Still if you are new to programming, welcome and don't give-up.
I run the www.learn-XNA.com site, over there we have 2 videos up so far. The first is about geting C# and MDX installed (pretty easy to do) and the second video was just put up today and it is the first of three videos on learning C#. The videos from www.learnvisualstudios.net are good too.
One good place to start is the Visual Studio Express Pages on MSDN, there is also a video series that you can follow that takes you through the basics of C# (http://msdn.microsoft.com/vstudio/express/visualcsharp/easytolearn/). In relation to XNA and MDX (Managed DirectX) you should have a look at www.thezbuffer.com. On this site The Zman has a good collection of tutorials and resources that target all levels. With XNA it will be good to start learning the basics of C# and MDX.