I recommend MVC.
You should consider starting with some of the information available from Microsoft: http://www.asp.net/get-started
WEB FORMS (aka Web Application)
Offers a familiar model that lets you reuse controls and incorporate
data into your Web site, making your work reusable and you more
productive.
MVC
Builds on a pattern that enables clean separation of concerns within
your web applications, and delivers full control over HTML for
enjoyable, agile development.
HOW DO I CHOOSE? Watch a 5 Minute Introduction Video
Visual Studio Express or WebMatrix ... how do I choose? Here's our
quick guide to choosing the right technology for your needs. You can
install everything or grab just what you want. This short video breaks
it down so you can pick the right technology and get right to building
great websites.