'New' at this, can you guys critique me?

[RalphDamiani]

It depends on what you want to accomplish. As for the actual method, it varies from artist to artist.
Here's my suggestion to you, it's usually how I work when using pre-made outlines (which is rare these days as I tend to sketch in Photoshop already):

1 - On your first layer, paint a quick background that resembles the one you want for the finished painting. You can always go back to it, so don't take too much time. This will also serve for your colour selection, since you'll be able to see how everything is working together. It will also save you the trouble of retouching your finished subject since you're already blending with the background.

2 - On your second layer, place your outline and switch the blending to Multiply so you can see your background behind it. Now, unless you want comicbook art or cell shading or anything where the outline is visible, I'd advise you to not paint on your outline, otherwise you'll have one heck of a job smudging all those lines. Besides, it's not a good idea to include true black on your shading, as it'll more often than not, look artificial.

3 - Use the third layer as your painting area. Start painting over the outline, using it as reference only. You'll end up covering details you need to see, but you can always toggle visibility on and off so you don't lose yourself. You may, if you like, use more layers on top of this one for different parts. It helps especially when you're still unconfortable with the brushes tool. Make sure you toggle "Use all layers" on your brush, so you get nice blending between layers.

4 - Use the first layer on the list for your palette. It's always a good idea to choose only a few colours to start with and after you decide the lighting of your scene, you can start blocking it out. It doesn't matter if you start with the light or dark, just don't try to mix in a wide variety of colours or you'll lose consistence over the scene. Alternatively, you can make your own colour selection with the swatches tab using the Preset Manager. Just remember to save it often.

5 - After you block your drawing, you can use soft and smaller brushes to blend the light and dark areas. From then, you can add more colours if you need. You may also use the dodge and burn tools, but be careful with them as they may produce artificial results. I personally prefer to use lighter or darker shades of the colour and control their opacity, painting over the areas that require more or less light. The trick is: Worry first about the shading, then you can worry about the colour. Some artists will paint in grayscale first so they get the shading right, as most things can look great with just one or two different hues.
Also, it's a good idea to paint with the opacity of the brush toned down. If you use a tablet, you can control the opacity using pressure points which produces the best results. If you don't have that option, avoid working with 100% opacity, so you can mix colours and enrich your texture.

6- Pick carefully the colours, there are plenty of tutorials around on the use of colours. But nothing works better than practising. You can also use photographic material. I recommend you spend some time mixing colours (using a low opacity brush) to get colours that are too hard to pick just by looking at the wheel. Simply increasing the brightness and darkness value of a colour to determine the levels of shading usually results in a poor selection.

Here's a screenshot of what I just explained above (begging your pardon for the illustrative paintover: ;))
http://xs305.xs.to/xs305/06336/paintingover.jpg

Hope it helps!
Ps: If you don't have a tablet, it can still be done. But it'll be really time consuming and not as precise.

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