Lets start with you floating still next to the ISS. The ISS is not big enough to have any kind of its own gravity so you cannot orbit it and will have to control your speed and direction all the way around it.
What you are going to use for this is the rotational and translational RCS thrusters. These control which direction you point and can also give you a little push in one direction or another.
The main controls you want to use(all on the numpad):
/ Switch between rotation and translation mode
In translation mode:
2 up
8 down
6 forward
9 backwards
In rotation:
2 up (like a backflip, this is technically called pitch up)
8 down (frontflip, this is technically called pitch down)
5 can be used in either mode to stop rotation.
Here is a couple pictures showing the idea:
So starting out facing the ISS you can press / to pick translation mode. It will light up LIN and say translation. Then press 2 a little bit to go up. If you start going to fast it will be hard to control your direction so take it slow at first.
As you drift up the ISS will appear to be going down so switch back to rotational mode by pressing / again. Then press 8 to point your nose down towards it. Just a little bit not to much so you don't start spinning out of control. When you are where you want to look press 5 to stop any rotation.
Now you should look like this:
Note that the 6 will still make you go in the direction your nose is pointing, not always to the left. So your velocity direction would be going straight up and now you can use a combination of 6 (forward) and 8 (down) in translational mode to stop.
Then use 6 and 2 to move across the top.
Continue along and change the direction your ship is pointing in to stay facing the station. Take it slow and keep practicing. It is easy to get out of control at first.
A good tip is that you can always bring up the docking HUD by pressing select below one of the screen displays, choosing docking with ISS as target and press the HUD button. With this HUD you can circle around to point at the circled crosshairs and accelerate towards them slowly until the number underneath goes to zero. This makes you stop moving in relation to the ISS.
Here is a little video showing it. I set it at 10X speed so the video wouldn't be to big.
You can use translation and rotation for any direction but I only put a few here to make it as simple as possible.
An good understanding of vectors will help out a lot with this and a lot of other things in Orbiter.