"Tentative itinerary is Frankfurt (flying into), St. Goar, Rothenberg, Munich"
Some tips for St. Goar and the Rhine...
Trains are great in Germany, including the most scenic part of the Middle Rhine Valley (St. Goar etc.) Train tracks follow both the east (right side) and west (left side) riverbanks and meet up in Koblenz at the northern end. Express trains connect the main towns, local trains stop everywhere. Here is a schematic train line map for that scenic zone; see the dark green line (RB10) for the east bank train stops, the light green line (RB26) for the west bank stops:
http://www.der-takt.de/fileadmin/_processed_/csm_Karte_3000_af861764b7.jpg
Once you are in St. Goar, you can do day trips from St. Goar using inexpensive day passes. A VRM "mini-group ticket" covers all of you for a day at a price of €23. Travel anywhere you like within the VRM zone (light green area.) VRM is the local transportation authority.
For day trips outside the VRM zone, use the Rheinland-Pfalz ticket day pass instead (€39/4 adults.) Travel anywhere within the larger R-P zone.
You can buy these day passes from a ticket machine on the day of travel for these prices. Very simple.
How do you get to St. Goar from FRA airport in the first place? If you look only at the DB website, you'll find a price of €82/4 adults for normal tickets on the regional trains. DB also sells day passes for weekdays (€68 for your group) or weekend days (€62.) But you can do better...
The price is only €51 if you buy two tickets... one to Bacharach (which is on your route) and another from Bacharach to St. Goar. Just go to a ticket machine at FRA's Regionalbahnhof station and buy one normal DB ticket for 4 adults between Bacharach and St. Goar (€16.40) AND one RMV group ticket (Gruppentageskarte 5 Personen, €34.50 at price category 6 for up to 5 adults) for FRA - Bacharach. (Note: Don't get off the train in Bacharach just because one ticket ends there - just have both tickets handy to present to train personnel.)
All the day passes and tickets mentioned above apply to the local and regional trains - be careful not to board any high-speed, long-distance trains (ICE, IC, EC, etc) at the airport or elsewhere.
St. Goar is a good Rhine base because of the ferry there, which runs all day long. Trains cannot cross the river between Koblenz and Wiesbaden, but the ferry landing across the river from St. Goar is within easy walking distance of the St. Goarshausen train station, should you wish to visit Marksburg in Braubach or the other east bank towns. See this St. Goarshausen town map. And you pay nothing for this ferry crossing if you have either the VRM or the Rheinland-Pfalz Ticket day pass in your hands - it's included.