Every MSDN page has a set of tabs along the top. These are the quickest shortcuts for finding learning resources, MSDN Library articles, downloads, and more.
The best place for asking questions is MSDN Forums, and here are good instructions for using the forums. Some of the forums have their own FAQs. Here is the FAQ for Visual Basic, for example.
MSDN is divided into subject-specific Developer Centers. Here is a map of our Developer Centers. Here is the Visual C# Developer Center.
MSDN features a lot of bloggers who write about what they are working on and what they are thinking. Check out our page of featured bloggers.
MSDN has hundreds of short videos that explain a wide range of development tasks. Here's a good start for diving into the "How Do I?" videos.