to answer your first question, ignore how far off the pointer is in stellarium, just get the star in the centre in your finder and then in your camera. once centered, it should stay there as you'll be tracking.
you need to hit ctrl+3 in stellarium to sync and add a sync point. you can verify the keys by looking at the stellariumscope window where it shows "listening".
http://stargazerslounge.com/uploads/...1363726447.jpg
the "key" in this window corresponds to the key sequence. ctrl+1 for slew, ctrl+3 for sync and ctrl+5 for cancel.
so once you center in the camera, make sure the star is selected in stellarium and press ctrl+3.
the scope indicator will move to the star and both will coincide.