Are the savestates of the different systems always stored in the rom folder?
For RetroArch based emulators, yes. Other standalone emulators may choose to save to different locations, depending on their implementation and it's not always in the system's folder (e.g. Mupen64plus, PPSSPP, etc).
How about dos games, are the savegames always in the folder of the respective game?
Most likely yes, by default the game folder is set-up in Dosbox as C: driver by default, so saves should go there.
If you're using a different set-up to start the games (using .conf file and/or a separate folder for PC games), then this may vary.
I'm not that big of a shell expert, the only thing that comes to mind right away is to copy the savegames and states by hand before mirroring them again so that they don't get lost. Does anyone have a more elegant way that is easy to do?
Use a NAS to share the ROM folders between the 2 systems ?
You can also use the roms share from one of the Pis as the network share for the 2nd Pi, using the same guide referenced above.