OK, well after a little trial and error, I figured it out.
Now that I've figured it out, I kinda wanna kick myself that it took as much trial and error as it did.
We know, by what's already been documented, that Overworld Character Palettes are located from 68200-6823F.
It took a little more searching to find the document, but I found a compilation of data by JCE3000GT from ~2003 that says the next four lines are vehicle palettes (68240-6827F).
Well, from there, all I had to do was scroll down a few lines, because then you've got four lines of FFs, then 24 lines of palettes, which belong to NPCs (they're easy to spot because they're 3BP, and therefore often start with 00 00 00 00).
Anyway, since NPC palettes are harder to define (they're more interchangeable than character or vehicle palettes, so you can't just say "it's Cid's daughter's palette," because she shares a palette with so many other characters), it takes me a combination of a screenshot, Tile Layer, and Yousei's SNESPal to zero in on exactly which palette I'm looking for:
1. take screenshot of an NPC that uses the palette you want to edit
2. find the corresponding sprite in tlp
3. use eyedropper on the first non-black color in the palette (as shown from left to right in tlp)
4. "edit colors/define custom colors" to grab the rgb value, and plug those into tlp to make that color the correct color
5. perform the same actions for the next five colors
6. jump to 682C0 (the first NPC palette) in SNESPal
7. scroll through the palettes until you find the one that matches the one replicated in tlp