I've played PCE-CD games via Mendafen for over a decade. You basically don't have to touch manually editing the INI if you don't want in the 0.9.x series, so long as you put BIOS files and such in the proper subdirectories.
Mednafen has no GUI so to speak (Inputs can be set up with graphical prompts while the emulator is running, however), but it doesn't really matter if you use it with one of the bajillion frontends that exist for most operating systems. Personally I use Quickplay and Mah!Cade on my desktop's Windows/Linux installs and GameEX on my Windows-based HTPC, which looks like this.
Probably on of the nicest things about Mednafen is that you can run games as CUE/ISO/OGG rips to save a metric fuckton of space. This is how big Rondo of Blood is in said format:
I believe the original BIN/CUE dump I had was a little over 530MB?
It's not very hard to convert a PCE-CD game to this format so long as it's a good BIN/CUE dump of a game. I wouldn't mind writing a detailed description of the process here if you'd want to utilize it.