People will tell you different things in regards to what sequence to paint the different areas of a figure. Some tell you to paint in the same order you dress, inside to outside. Others will tells you to paint in the same order that you would color with pens, from darker colors to lighter colors. I tend to paint largest area to smallest area because for me this is the fastest. You will have to experiment and see what is comfortable for you.
When picking color schemes, I look for colors that will contrast with each other. This makes the colors stand out on the tabletop. I like red-green, yellow-purple, yellow-blue. white-red, white-purple, etc. My Skaven are another example. I paint armor and fur fairly dark colors, but I paint their hands and feet magenta and highlight them with pink mixed with a little white. This adds a splash of color to an otherwise drab army and makes them stand out.
What order should you paint your basecoats? For speed reasons, I start with the areas that will get the darkest washes. For me, that's anything that gets washed with Liquitex Paynes Gray (i.e., blues, grays, armour, reds, and dark greens). I paint those basecoats, wash, paint the next lightest set of basecoats, wash, then finish with faces and hands. By using this progression, I avoid having darker washes bleeding onto lighter basecoats.