@deodekabokat If you're on the command line, you can use mc (maybe you're familiar with the Norton Commander/Dos Navigator/etc. interface) and navigate around the filesystem.
Otherwise, you can copy the file on the ROMs folder and look at it over file shares
cp /etc/emulationstation/es_systems.cfg $HOME/RetroPie/roms
I'd advise to use the full image - and not the Berryboot variant - if you can spare a SD card for a few days while you tinker with RetroPie.