Baden-Württemberg takes up much of Germany's southwest corner:
https://cdn.britannica.com/34/114934-050-A42B2937/Baden-Wurttemberg-locator-map-Germany.jpg
Have a look at also at the railway density within B-W below:
https://karteplan.com/deutschland/land/baden-wurttemberg/schienennetz-karte-von-baden-wurttemberg.jpg
The Black Forest, which makes up most of the SW quadrant of B-W, is well-covered with railways too:
https://prospektbestellung.toubiz.de/media/prospekt/file/5736289_KONUS_GB_2022.pdf
Service is frequent and dependable, though sometimes there are delays. So the short answer is "Yes." You can easily visit the Black Forest across 7 days by train, and you will still have many nice destinations left over for additional train-based visits on future trips.
The problem with suggesting places to visit is that there are way too many candidates competing for your time, and we have no idea what interests you. Also, there are dozens and dozens of nice places in the remainder of Baden-Württemberg that might interest you as much or more than those in the Black Forest.
The 3rd link I provided explains the KONUS program - obviously, the free train travel within the BF is an advantage there.
I suggest you check out a Germany travel guidebook like Fodors or the Rough Guide or whatever you can find at your local library and check into their recommendations for Baden-Württemberg area to see what interests you most. The RS Germany guidebooks don't go very deep into individual German states in the way that the more comprehensive guidebooks do. Once you know where you are going, you can work out the transport details.