I'll preface this with my pet peeve about the move - it's half a controller. You still need the navigation controller if you want to play comfortably (although sixaxis can be used, it simply isn't nice to do so). You also need the PSEye so pick up the starter pack if you need that as well.
It's suprisingly accurate, and combines very well with the Ps3 Sharpshooter (which isn't just a plastic housing but another circuitboard driven product which remaps buttons to more ergonomically desirable positions for gun games).
The best games to go with this are Goldeneye and Sorcery which are stand out. If you've got a 3D tv this also works superbly with Resistance 3 - it really adds to the realism to shoot with a move/sharpshooter combo on a big 3D screen. If you haven't tried this, find a friend with a big screen TV and have a go because it is the best showcase the ps3 has.
The move device is a great tool, has solid battery life via integrated battery but it's a pain to keep everything charged. The move and nav parts need charging seperately, and the 2 USB slots on the ps3 make this a juggling act when combined with normal controller and plugging in the ps3 EYE you need to use this. Invest in a wall charger to go with the move if you don't want this headache.