If you are a professional ASP.NET developer, and have some time to spare on learning new stuff, I would certainly recommend that you spend some time trying out ASP.NET MVC. It may not be the solution to all your problems, and there are lots of projects that may benefit more from a traditional webform implementation, but while trying to figure out MVC you will certainly learn a lot, and it might bring up lots of ideas that you can apply on your job.
One good thing that I noticed while going through many blog posts and video tutorials while trying to develop a MVC pet-project is that most of them follow the current best practices (TDD, IoC, Dependency Injection, and to a lower extent POCO), plus a lot of JQuery to make the experience more interesting for the user, and that is stuff that I can apply on my current webform apps, and that I wasn't exposed in such depth before.
The ASP.NET MVC way of doing things is so different from webforms that it will shake up a bit your mind, and that for a developer is very good!
OTOH for a total beginner to web development I think MVC is definitely a better start because it offers a good design pattern out of the box and is closer to the way that the web really works (HTML is stateless, after all). On MVC you decide on every byte that goes back and forth on the wire (at least while you don't go crazy on html helpers). Once the guy gets that, he or she will be better equipped to move to the "artificial" facilities provided by ASP.NET webforms and server controls.