You should be seeing 13.6-14.6 volts. When you first start the car, the voltage will be lower as the current ramps up to recharge the battery, or if you turn on accerssories like you say.
If you running voltage is always high, around mid 14 and you are having trouble starting, you likely have a battery problem. The voltage goes up becuase the alternator is trying like hell to recharge that battery.