I've noticed a few things (for the purpose of testing I've been trying ROMs that have worked previously on Genesis Plus GX - so pardon me if PicoDrive has different requirements or if there are reasons for this not working yet - such as perhaps a premature initial port) -
There doesn't seem to be support for the extension 'md' (either in pico/cart.c, pico/media.c and/or platform/libretro.c). This should probably be added since a quite popular romset has all its ROMs with that extension.
Nearly every ROM I have tried so far returns 'PicoDrive: failed to detect ROM/CD image type. RetroArch [ERROR] :: Failed to load game'. I have tried ROMs ending with the .BIN extension and .MD roms (after adding 'md' to the list of supported extensions myself in pico/cart.c, platform/libretro.c and pico/media.c, but still the same problems).
I've noticed a few things (for the purpose of testing I've been trying ROMs that have worked previously on Genesis Plus GX - so pardon me if PicoDrive has different requirements or if there are reasons for this not working yet - such as perhaps a premature initial port) -
This is on x86_64 Linux BTW.