If you are not arriving from the North, a good way to start a visit of the Rhone Valley is starting from the South, in Avignon.  It is a quick 3 hour 20 minute train on the TGV from Charles de Gaulle and there are many things to do in this major city, the least of which is visiting the Palace of the Popes.
InterRhone, the Rhone Wine Council, is based in Avignon, so prior to heading out to wine regions, you may want to stop here first.  There are many resources such as maps …