Tom-Fu

Please keep in mind that the following are all very generalized thoughts on and techniques for miniatures painting that I have developed over the years. They work for me. They may not work for you. There will always be situations in which this advice does not apply. Use your own imagination, and experiment with techniques and colours. There are many ways…This is but the Way of the Exploding Pudding. Remember, the bristles bend in the stroke, but do not break, so must also you do, Little Bag of Rice.
And always remember, My Kung-Fu is the stronger Kung-Fu.
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Jewels of Wisdom:

Overstate it.

If you look at a person standing about 20 metres away, that person will be about the same size as a miniature close up. Now see what details, colours, highlights and/or shadows are noticable.
That's right, most colours are drab, you cannot really discern the eyes or other smallish features, and no real highlights are to be seen unless the sun has put it's hat on and has come out to play -in which case the person will be about half very bright and half very drab, or one of the above depending on the angle.
In miniatures terms: if you paint a figure like that it'll look terrible! What you need to do is simply to overstate it! Use stronger colours and higher contrasts than would be "natural". Very deep shadows, very bright highlights are the way to go.
Remember that colours always seem darker on a small surface than on a large one.
 

Keep it simple.

It is usually a good idea to keep the main colours as few as possible (three or four usually do the trick). To many colours tend to make the figure (or the viewer!) go into "kaleidoscope seizure", and seem messy.
 

Keep it neat.

This is perhaps the single most important piece of advice, so heed me, and harken to my clarion call. Nothing can ruin an otherwise well painted miniature than colours that "cross the borders", such as flesh colour getting on the the sleeve of an otherwise white shirt, eyeballs going all over the place, or base green riding up the boots.
Make sure that all colours end where they are supposed to end, with straight and sharp edges, and you are a long way to miniature greatness. A good way of doing this is by the technique called "Black Lining" -simply painting a thin black line on all the colour edges.
 

Use a large enough brush!

This is very important. A common mistake is to use a too small brush. What usually happens is that the paint starts to dry before you are finished applying the coat, and stripes and lumps are created when you happen over the half dried paint. This is very unsightly and ruins alot of good paint jobs. Also it takes more time to apply a coat with a small brush.
If you use a large enough brush this usually does not happen as you finish applying the coat much faster. Just be careful to avoid clogging up any detail.
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Get me outta here!