Sure. The simplest approach is to use a naive Bayesian classifier (you can find a bunch of open source implementations).
In my app, I actually track client-side actions -- essentially, clicks, but with more context. Anyway, you can treat a single user session like you would the text of an email, where the "actions" are the words.
From there, all you need to do is capture a bunch of sessions and tell the classifier which users are not strong computer users and which know what they're doing, passing the corresponding "documents".
Now you can feed in new documents and determine which of your users know what they're doing, and which aren't really computer users.
(It my experience, people fall into one of those two camps.)