Learning a new programming language or technology is for one of three reasons:
1. Need: you're starting a project for building a web application and you don't know anything about ASP.NET
2. Enthusiasm: you're very excited about ASP.NET MVC. why not try that?
3. Free time: but who has that anyway.
The best reason to learn something new is Need. If you need to do something that the .NET framework can't do (like performance for example) then WinAPI is your solution. Until then we keep ourself busy with learning about .NET
