Go and look at some really well painted figures on various threads here on Armorama, on Historicus Forma, and in the Missing-Lynx Constructive Comments and Figures forums.
(There are other places on line, but these should get you going.)
Note the techniques used by the various painters of the figures you think are the best.
There are two major "schools" for figure painting - 1) All acrylics using "glazes" for shadows and highlights, and 2) Artist oils usually painted over acrylic undercoats and blended "wet-on-wet."
Some few painters use acrylics and glazing for uniforms and oils for faces and hands. A very few still use hobby enamels blended wet-on-wet (or semi-dry and sometimes combined with artis oils).
Of the these techniques, I can say that I use the second basic method, artist oils over acrylic undercoats, but there are some phenominal figure painters who use acrylics exclusively, and still others who use other techniques.
Next, go and get a couple of books on figure painting. Osprey has several pretty good and relatively inexpensive books. Look for authors like Mark Bannerman and Calvin Tan (again, there are others).
Note that the authors of any figure painting books you buy will only be showing the techniques that they use,so if you want to learn how to paint using acrylics, you should look for books by authors who paint using only those (Calvin Tan comes to mind). (Mark Bannerman is an "oils over acrylics" painter.)
You'll note form the above that most figure painters use some acrylics, either exclusively or as undercoats, so learning how to thin and paint with brands such as Vallejo, Andre, Games Workshop, Reaper, etc, is your first step in developing your painting skills.
Once you can get consistant results with mono-tone colors on your figures (i.e. the uniform items painted in single colors with no shading or highlights), then you'll be ready to take the next steps of highlighting and shading.
You need to develope the brush control needed to get smooth applications with sharp color demarcations. You need to be able to brush fairly fine lines and small details with sharp edges and color demarcations. These are the basic brush control skills that you must master before being able to get good results with any shading techniques you want to learn.
You also need to learn how to thin and mix the paints. Most acrylic paints should not be painted straight from the bottle, but rather thinned and applied in multiple semi-transparent coats.
BTW: These same brush control and "paint management" (thinning and mixing) techniques are the ones you need to do good detail painting on your armor models.
You can take your mono-tone figures and dry brush and apply washes to get some shading, but dry-brushing and washes will only ever take you so far. However, a lot (probably most, really) modelers are satisfied with just mono-tone colors, dry-brushed (for highlights) and washed (for shadows).
Once you're ready to go beyond these basic techniques, though, you'll need to pick one of the shading techniques used by the more advanced figure painters and learn it.
Here are some of my figures:
I clean-up and assemble the figures as completely as possible before I paint (because I hate to have to go back and do touch-up painting). However, I almost always paint the heads and faces separately because it is so much easier to access them.
I prime with Tamiya flat white sprayed on with my airbrush. Nothing special here, just an even flat white acrylic base. This helps to show areas that still need work (cleaning, seams, filling, etc) and provides an even color to paint over (so that the underlying color doesn't effect the final colors).
I undercoat the figures using mostly Vallejo acrylics matched or mixed to a color close to the desired final color of the item.
I then use artist oil paints, colors mixed and blended on the pallet. I paint the figures entirely with the oils blending the shadows and highlights on the figure. I like oil paints becuase of their versatility in color mixing (I don't need to buy every acrylic color under the sun to get the right shades on y figures) and their long working time which makes blending them easier.
The long working time means that they take a few days to dry (considered by many to be a draw-back). Also, some practice is needed to blend colors (an easily learned skill), and finally, some practive is need to learn how to apply oil paints (very, very little paint is needed!).
After drying (usually a couple of days under a cover to keep the dust off), I do any final assembly (usually just adding the heads) and then flat coat the figures with Testors Dull Coat.
As you develope your figure painting skills, everyone here on Armorama will be happy to help answer any questions or offer more advice. But you really do need to be clear in your own mind about the techniques you're trying to master or the answers and advice will often sound conflicting and be confusing. This is because everyone has their own techniques and many of those are not necessarily compatible with other techniques.
What works for one painter often times cannot be combined with what works for another. It's up to you to keep these straight.
HTH,
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