usually i go from shadows to highlights it easier for me to figure it out that way!
i usually undercoat my heros either a light tan/leather brown or white to start. this will make the colours brighter and pop a little, then i will wash the entire figure with an ink mix that is sort of a purple burgundy colour, this will act as the recess shadows and darken down the base coat.
then i will wet brush on the first coat of colour, usually a darker version of the colour i want. wet brushing is just like dry brushing but with paint on the brush, not that much, just enough so the brush is loaded but you can still see the hairs and it holds its shape. then i will work the colours up in stages with a mix of the colour i just put on with a lighter version. i like my paint quite watery, that way i dont loose detail, but i may have to apply more than 1 coat. also as you are doing work colour to colour, so if you paint all the red, then all the blue and so on, this keeps colour continuity and saves paint! also i use the side edge of the brush and not the tip, and gently stroke over the model(i could be rude here but i shall rise above it) remember that the detail is already on the model u just have to bring it out and exaggerate it.
most importantly experiment and have fun, i paint very differently to my friends as they do to each other, we all have our own style its just finding what works for you and what you like!
also i will post a few pics up for you to try and show what i mean!
