Well everyone at work uses it, so the best way I use it to discover music is to actually listen to each other's playlists.
To share a playlist just right-click on the playlist click 'Copy HTTP Link' and IM the link to a friend.
Other than that I just basically search for genre, i.e. 'acoustic', order by popularity and let it play.
They also have Artist radio (which I don't use very much), which basically looks like listening to a random set of tracks from similar artists.
I've actually discovered a lot more music I like on Spotify than any other service for a long time.
It's actually that good a service that I'm probably one of the few people paying the monthly £9.99 p/m to listen to music without interruption, as I think the service is actually worth paying for.