A short update from my adventures with a second floppy controller!
I got two additional Goldstar Prime 2C controller cards for really cheap. On it's own every controller is working fine, but two together won't work, I tried different drives, different orders of the cards and drives and different options in config.sys.
But nothing works, I now gave up on the idea of using two controllers and settled on a comprise:
A hardware switch, similar to the "two drive monte" described here:
https://www.seasip.info/VintagePC/floppies.html
Attached is a photo of my little splitter I soldered up real quick.
It basically interferes with the drive select and manually switches it with a switch between the two drives attached to the splitter.
The only drawback is, that I can't use them at the same time, but that's ok, as long as it works reliably.
I didn't bother to interfere with the motor signal, so when a diskette is inserted on both drives, both spin up. But that's a good tradeoff to only have to switch around one signal. It's of course possible to switch that signal too.
(If someone needs a schematic feel free to ask!)
Thank you alot for your advice!