I think the best way to find a color scheme that suits the mood of the scene or the location. I'll use a comic page of mine as an example.
The location is a stormy mountain, so the over all colors are blues and purples, even though the characters have their own specific color scheme. The blonde character's hair is brown if you use the color picker, but looks blonde in comparison to everything else.
A little more advice could come in the order in which you do things. I understand the feeling of wanting to get to the coloring and the shading right away, but it is better to finish sketching then move on to lining then move on to coloring then move on to shading and highlighting.
Also, instead of cleanly coloring within the lines at first try, messily filling in colors until you get the ones that fit the mood, local, and characters works well too.
Lastly, using an overlay or hard light layer of the most common or most important color over all other colored layers can really bring a scene or setting together. And @keii4ii
is right, having all the colors on a character or in a scene be very saturated is hard to look at and can be distracting for the reader. But it's all a matter of preference and what works well for your story.