To 'pull off the road' means to leave the road - your first meaning.
So - you can pull off the road onto the shoulder - e.g. to drop off a hitchhiker.
You can pull off the road into a carpark.
You would not usually use it to mean turning into another road.
It's a pretty common phrase - no context is needed!
The other meaning relates to objects - e.g. you can pull the lid off something. You can also pull a dog off another dog!
You would only use it in this way if the car was broken down, AND you were pulling it (rather than pushing it) e.g. by towing it with another car. But that would not work in your example, as it does not fit the context.