Don't confuse uv mapping and texture creation/painting. Uv map defines how the texture image is "put" on the 3d geometry. It maps 2d image onto 3d object. This is done using u and v coordinates of vertices - each vertex has it's position in the 3d space, and it has it's position in the 2d texture space. You can see and edit vertex position in texture space in the uv editor.
But you don't really need texture image in order to define the mapping. By editing uv coordinates you just specify how the mapping operation will be carried out, not what will actually be mapped.
For example in quake 3 arena, Cadaver and Biker are same mesh with same uv layout but have different textures painted on them. 3d artist made the model and uv layout and then texture artist painted different texture image for each villan using same uv layout as a reference.
Usual workflow goes like this:
Ediu uv's, project, move, combine etc ( whatever your tool of choice has to offer ) until you get nice "uv layouts" ( nice means something that is good for painting ). This requires little bit of forward thinking.
Snapshot the uv layout and paint the actual texture over layout in paint program or directly on 3d geometry if your 3d tool has this ability.
Basic concept is really straghtforward and you can learn most of techinques from manual of the tool you'll be using for laying out the uv's. There is really no point in learning it if you don't have some kind of uv tool to immediately try out things.
For polygons there is no alterantive to uv mapping.
In my experience, editing uv's is at least as hard as doing the modeling. And you need to be creative and have decent problem solving abilities because there are no rules on how to do it properly.