Okay, so I couldn't find an unpainted figure to take photos of, but I did find a clip-art picture of Thom Yorke to show the process on, because a model is basically a three-dimensional colouring book. In fact the basic aim is the same in both cases: to create and exaggerate the sense of depth so that all the features are discernible.
Caveat: I'm not a serious figure painter, nor do I follow their recommendations to the letter. If someone else says I'm doing something wrong, you should probably listen to them.
To start, as I said before I use acrylics. There is no best/worst type of paint to use, it's whatever you prefer. Enamels like Testors and Humbrol have the advantage of being 'blendable' because they are slow drying, but you will need to use an appropriate solvent instead of water to thin and clean your brushes. It is possible to put acrylics over enamels or vice versa as long as you allow the bottom layer to dry completely. You can use oil washes over acrylics or acrylic inks over oil if you follow this rule.
Pretend this is an assembled model:

First thing we do is look at the figure and see which parts are the most recessed and which parts stick out the most. It's easier to paint raised details, so we'll start with the recessed stuff. That way we can be messy and cover things completely and then have an easier time painting the top layers. In this case, the skin is the lowest layer, with the shirt, jacket and hair all on top of it.

I always prime my figures to make sure that the brushed layers of paint adhere well and to provide a uniform base colour that helps you see if you've missed spots. The three most popular colours are brown, black and white. You can spray it with an airbrush or use a spraycan; it doesn't need to be special primer, just make sure it goes on thinly and doesn't fill in any details. For my actual figures, I airbrushed Tamiya black acrylic because it has good 'bite' and doesn't rub off as I'm handling the figures

We start with the skin, no need to be very accurate on the first few blocks of colour. Depending on the particular tin of paint, you may need to thin it a bit to get it to go on nice and smooth. Not as much as when you're airbrushing, though! Paint that's too runny won't stick and will fill in the lowest recesses only. Even within the same brand, different colours come out of the pot differently, so you'll have to experiment a bit. I usually just dip my brush in paint, smear a big drop on some plastic surface then rinse it off, dampen it with clean thinner and mix that with the paint until i see it flowing nicely and still providing good coverage
more to follow in another post!