"Russ, are you suggesting that we base ourselves in one place (other than Bacharach) and then venture out each day for the excursions?"
Actually, with 4 full days, I just sort of assumed you would be making such excursions from Bacharach. I like St. Goar and Boppard a little better for location and logistics, especially for train travelers like me. It's more central. But outings are doable from Bacharach as well.
"We'd still like to stay a couple of nights in Bacharach though because it seems like such a lovely, quiet town."
It's a lovely town. It's fairly quiet in some spots, but the position of the town so close to the tracks has made for a whole lot of upset visitors (and townfolk.) The Kranenturm Hotel is one of those that gets huffed and puffed at with passing trains: http://www.rhein-zeitung.de/cms_media/module_img/1195/597502_1_arslideimg_597502_1_org_bacharach.jpg
The town is wedged between the cliffsides and the railway:
https://upload.wikimedia.org/wikipedia/commons/8/81/Bacharach_Luftbild_01.jpg
Train noise can be avoided to some extent if you choose a Bacharach location carefully - the Blücherstrasse locations just up the little valley, near the church, don't get so many complaints. Check the reviews carefully if you want to stay there. Noise is not unique to Bacharach but it's generally worse there than in St. Goar and Boppard. All the towns are subject to road noise and some river boat noise as well.
I like staying right in town myself. With a car, you might want to scout around for a location outside of town in the hillsides for more peace and quiet. This winery/hotel outside Oberwesel is just an example, not a personal rec.: http://www.gasthaus-stahl.de/hotel/?lang=en
"Is Mainz worth some consideration?" The sights and museums in Mainz are interesting, and it has a huge pedestrians-only zone for shoppers and sightseers.
https://www.tripadvisor.com/Attractions-g187393-Activities-Mainz_Rhineland_Palatinate.html
Mainz' open spaces are nice too - the Market Square,
Augustinerstrasse, the main pedestrian artery through the old town, Mainz' Stadtpark are all nice spots. But it's nothing like Rothenburg, if that's what you mean/what you want.
An outing I didn't mention is the one to Bad Sobernheim for the Open-Air museum there - you really get an interesting look at what life was like for locals in recent centuries at this place. Here's the museum homepage. Bad Sobernheim means an outing up the Nahe River Valley, where there are some other towns you might like, including the gem-town of Idar-Oberstein and Bad Kreuznach, with its cute old town and bridge houses.