They're great for interfaces (where you can add "composite" behaviour which only uses existing methods on the interface) - LINQ to Objects is the prime example of this.
They're also useful for creating fluent interfaces without impacting on the types that are being used. My favourite example is probably inappropriate for production code, but handy for unit tests:
DateTime birthday = 19.June(1976) + 8.Hours();
Basically anywhere that you don't want to or can't add behaviour to the type itself, but you want to make it easier to use the type, extension methods are worth considering. If you find yourself writing a bunch of static methods to do with a particular type, think about whether extension methods wouldn't make the calls to those methods look nicer.