People have been asking me for a 32 color palette, but I figured I'd make it easier for me by just expanding on the old 16 color palette (not allowing myself to change those). That palette was focused on RGBO and several darks. It was missing CMY hues, a skin tone (sacrificed it for the yellow), some greys and more strong graphical mid-tones usable for text and such. The first step was to just fill in those gaps, so I did that and then started nudging the colors around, but it's hard to tell at this point if the colors are usable.

Comments:
Two grays at the either side of the old one. Note that the darker gray is a bit colder to meet up with the other dark colds. Unsure what this does to its role as a bridge color. I haven't really checked how these gray values ramp into other colors.
A wine red / dried blood red which I figure could be useful. Different from the old-poop brown, but perhaps the dark-pink later gets a bit too close for comfort.
A more bold orange for explosions. Fits into the brown yellow ramp.
My favorite yellow! Maybe even my favorite color.
Now, the requested purples. And three of them! I'm quite unsure about the values for these, but would like them to play well with ramps and maybe even fit into a skintone ramp (or as saturation points to spice up skin tones). Also, I felt that the old palette was very focused on darks and brights so I wanted some mid-tone colors. I'm thinking, Kirby-type creature light and shadow, or something like that. It's sort of hard to tell how well these work without doing some mockups or manual indexing of existing game screens (black BG games will work differently from say, sky BG games like Mario). I'm worried that the dark-pink is too close to the red. I added a colder version too, simply because it was missing.
The promised skin-tone returns! I want this expansion to be Eroge-certified! Unsure how it will handle darker tans though. Or tan lines! I suppose the lighter pink could be put a value notch above the skin-tone rather than below because tan lines are often colder in tone, but... it seems to be more useful as it is.
Cold green to fill in the green ramp. Could be colder.
Two teals. Just added them to fill in the blank slots, unsure about their use.
A purple dark blue, just because the old one was so green (meant to be used for water).
A regular blue to plop into the blue ramp. Could be a tad more saturated perhaps.
Two muddy yellows that I hate, but they fill in a missing part. Maybe usable for burnt grass and such. Maybe the dark one should have a Metal Slug hue?
--- That's it. The tricky part about multipurpose palettes like this is that it's tempting to change a color because it works better on a single test (or because it looks "new" and you forget the use/justification of the old version). I think I'll do some tests manually re-indexing some game screens (Photoshop is kinda crap at indexing). If you want to fiddle around with it, feel free. I don't know which role a lot of these new colors could play, but my hope is that they make non-black BG games more feasible.