I've never been that great with watercolor, so I can't answer everything with confidence (and I'm brand-spankin' new to the forums, so someone more knowledgeable may very well post before moderator approval of this)--but I'll offer what I can!
You might be able to fudge it with watercolor pencils and just enough water to move the pigment? But I never had luck preventing warping, so I'm not sure.
Ink after. You might be able to ink first if it's waterproof--but it still has a chance of bleeding, so it's much safer to do a light pencil sketch, do the colors, and then ink after you've let it dry. That also lets you use the lineart to cover up potential small mistakes made while coloring.
I don't see any of the base portraits, but google gave me a post with the Critical Role ones at a larger size than I've seen in-game: https://critrole.com/deadfire-watercolor-vox-machina-portrait-reveal/
If you have rubber cement, you can use that to block out spaces you don't want the watercolor to go. Masking fluid is the specific material made for use with watercolor, but they're very similar--you paint them in the area you want to avoid color on (either in lines or blocked out areas), let it dry, paint what you want, and after that's dry, gently rub off whichever you use with an eraser. Crayon might work in a similar, more permanent-on-the-page manner, but also less effectively--I'm pretty sure the watercolor would seep through some.
Bonus: start with light colors first. If you start with dark colors, they will be much more likely to bleed into the light ones, and it'll cause undue struggle. Consider testing, both in general swatches and on sketches--do not be afraid to do multiple attempts of your portraits, if you have the materials. Practice until you're satisfied.
Bonus 2: looking at the larger Critical Role portraits (and judging by the total amount available), I'm pretty certain they were all done digitally. Keep that in mind regarding your end results, especially (I think) the colors and precision--don't feel like you have to use a pure, untouched scan of your work when you're done. Adjusting colors, details, or doing edits digitally is absolutely within reason, and not cheating in the least. (Harder without a tablet, boy howdy do I know it, but still feasible if you need to.)
Best of luck! It's so rad that you're doing actual, physical watercolor portraits. :D I can't say how long I'll lurk of these forums, but if I'm still around when you're done, I'd love to see your results!