Possible Duplicate:
Biggest advantage to using ASP.Net MVC vs web forms
Which would you pick if developing a new application?
Possible Duplicate:
Biggest advantage to using ASP.Net MVC vs web forms
Which would you pick if developing a new application?
MVC is a framework that sits on top of ASP.NET. What you should be asking is should you use Webforms VS MVC. Watch some of the getting started videos at http://www.asp.net/mvc and see which one you like more. You will need some VB or C# experience, so learn one of those first. Good luck!
MVC3 because it gives you everything ASP.NET gives you... plus a WHOLE LOT MORE. Also, MVC3 does not prevent you from using ASP.NET.