If you have a proper thermostat for the air conditioner, just set it to the temperature you want; it won't cool down faster with a lower thermostat temperature setting.
What I generally do when driving is use the vehicle air conditioner and have a rear ceiling vent open (one with a vent cover over it) to help pull the cool air through the vehicle. The truck air conditioner is theoretically a good bit more powerful than a roof air conditioner, though it's somewhat limited by what sort of airflow you can get through the coils (and not helped by having the ductwork directly above a big hot engine). I think it's somewhere in the vicinity of 25,000 to 30,000 BTUs.
Upon arriving at a camp site, if the interior of the RV is hotter than the outside air, opening the vents and windows will cool it down rather more quickly than an air conditioner can. I'm not sure running the air conditioner during that time has much bearing on things; the basic goal is just plain old air exchange. Maybe runnign the air conditioner's fan would help in some cases.