Just completed my first orbital rendezvous and docking.
here's a quick rundown/guide to what I did, there might be some handy hints for people in here.
The station hub was in a 100km orbit, and i got my ship into a ~77km orbit. Set the station as the target, and then picked out the best spot to place a maneuver node so that when I made an elliptical orbit I was getting pretty dam close approach distances with the station when i intercepted the orbit, without going out to much further, to minimize speed difference at closest approach. I also corrected for inclination at ascending node. Ideally, in kerbin orbit at least, you want to get a minimum of perhaps 3-5km (i got 2.9 for this case), but less is always better.
Once you reach the closet approach point, make sure the speed reading is set to target (it should auto change). this reading is a speed relative to the target, and the navball should change showing you this direction. Burn opposite to it at the closest approach to get the reading down to zero. After that I did a small burn towards the station and slowly made my way to it, slowing down when I got there. This isn't the most efficient way, but i think its the easiest with the tools we have in the game currently.
For docking, I found that the easiest way to dock is to like up parrallel to the docking port, put ASAS on, and then use the RCS translation keys to translate. The SAS will keep the craft orientated in the same direction, which is very handy. If you want to try docking without RCS, you're a crazy person.