Here's how I make a more interesting palette for drawing, starring Pichu. There are more ways to express "red" by picking "RED"! Redefine how you see colour to make an image that grabs.

Making good inbetween colours is a lot easier if your program has blending functionality, Paint Tool SAI does this. Or you can utilize online programs such as
http://meyerweb.com/eric/tools/color-blend/#:::hex

also try net palette generators for getting the hang of what look good together, I like this one!

(If you're actually using MS Paint please consider upgrading to GIMP, it is basically a free photoshop)

(I'm think that what I called tertiary is supposed to be analogous ...?)

Sorry if it is hard to understand, not too good at communicating ideas other than pictures (o o;)

TIP: Try not to use a pure black or white in palettes, instead, try doing highlights with a very light yellow or maybe cyan? it depends ..

when i made this my monitor was really shitty and dark so I didn't pick the right hue sometimes