In most cases you can fill one tank while using the other. It may depend slightly on how the propane system is plumbed. Many RVs with dual tank setups have an automatic switchover device that uses propane from one until it's empty and then switches to the other, usually with a flag or other indicator to show when this has happened.
You can fairly accurately determine how full a tank is by weight (subtracting the tare weight, which should be stamped or marked somewhere on the tank) or by observing the line where the condensation or frost reaches while in use. If there is no such line, pouring a little hot or very hot water on the side can often encourage it to appear. You do need to be using propane, or have used some recently, for this to work; it's based on the cooling of the liquid propane when the gas boils off.
In terms of efficient refilling, if you have 20 lb tanks, avoid the exchange places if possible. Most of the exchanges do not put the full 20 lb in the 20 lb tank, often only around 15 lb. (It is true that you can't fill a propane tank to the tippy-top, but a 20 lb tank is designed to hold 20 lb with the appropriate extra margin for expansion. If improperly filled all the way up, it would hold about 25 lb of propane.)