I agree...both of these technologies are useful and worth learning today.
If you've spent time building UI's in Windows Forms, you may find the event-driven model of Web Forms more comfortable. Since the Web Forms technology was designed to abstract away the HTTP/browser stack, you may find that this enables you to get down to business pretty quickly. In addition, the supporting tooling, documentation, and training resources are very mature. That said, you can find yourself hitting the wall pretty quickly with this model once things get complex.
MVC may involve a little more work up front getting to know the composite parts, but it gives you a lot more freedom than Web Forms in controlling the output. You will take on some more responsibility of learning how the HTTP and browser stack work, but the tools will get in your way a lot less. The tools also tend to enforce much cleaner separation of concerns in your code, making for easier testing and debugging.