If you have integrated Unit Testing in Visual Studio (I think it's part of Professional and better), start with that, because it's integrated. Downside is that to my knowledge, there is no test runner outside of Visual Studio or the Team Foundation Server which disqualifies it for automated testing, but I am not sure how current that information is.
Other alternatives are xUnit.net, NUnit and mbUnit. I can't really talk about the pros/cons due to lack of experience, but I use xUnit.net now because a) I know that there is a working ASP.net MVC Template since Version 1.1 and b) Assert.Throws is just sexy. I use the free personal version of TestDriven.net as my Test Runner within Visual Studio.
There is a "How to get started" Guide for xUnit: http://www.codeplex.com/xunit/Wiki/View.aspx?title=HowToUse
Again, I can't really compare them due to lack of experience with NUnit and mbUnit, but I believe that all three are quite stable and usable.