Jeff and Joel discussed this on Episode #32 of the Stack Overflow podcast.
Essentially, it's a vocabulary search - which other posts have the same vocabulary as this one.
Of course, there's a lot of tuning involved - the top 10k most common English words are excluded, and tags are included, plus (probably) some magic sauce they haven't revealed.
As far as I've heard, there's nothing you can do if a a question on the list is really unrelated, as the matching is entirely automated, done in real time (no preprocessing, means nothing to tweak).