1st if the PRV is dripping it will need to be changed if you can't stop it by turning the knob a few times.
The other leaks on the boiler need to be cured as you say.
If the pressure is dropping with the boiler valves shut, although if the boiler is loosing water I can't see how you can test, then you also have a leak in the system, check all the radiator valves and nuts first.
If there's no water in the expansion vessel then you just need to top the pressure up to 0.75-1bar depending on the size of the system.
Quote:Would I be correct in thinking that if water can leak out of the two spots mentioned above then so could pressure from the Expansion Vessel?
No the air in the expansion vessel is sealed from the system, unless the vessel is duff. (water when you press the little valve)