short tip:
if u're lucky to have set up the model pose mode with arms an hands horizontal (while is worst for later rigging) , you can use a plannar 2 sided mapping. Then the key is :
-go "spreading" the vertices in the visible areas where it does tangle coords. That is, exterior borders of the fat finger and the nearer one. Also in the thinest. And even in those, only in the exterior broders. As the inside borders are covered usually by other fingers. That's quick to do. Alsospearate/spread the tip coords, to give em a less distorted mapping, just is go separating vertices, giving it like an "exploded" expansion, u keep so more or less the actual proportions of each triangle.Not one by one thing doing the same, but more or less separating them the same, in an ordered net.
Final result is like if fingers had expanded.U could do this with all fingers, but no need as I told u. Mainly the 3 ones I told u, and even so , only in the "walls" that will be seen.
for selecting the vertices in the inside walls that get tangled (as are the sides in fingers, and are non paralell to "camera") you use better the split in 2 type of viewport organizations, u have an icon in the toolbar for this. Is easier, as u can select the vertex in 3d view, and separate it cleverly in the uv editor 2d window, ok?
If the arms are not horizontal, but in better for rigging 45º, then u do this same, but the first space will be camera mapping just rotating world in the 3d window till u have the hand paralell to you, so u see it well. uvmapping-->camera. Same with the back of the hand.uvmapping-->camera.
For selecting this tangeld "walls" vertcies is not so complex, as usually fingers are pretty low pol. I can uv map a hand in almost no time so, and usually ingame is seen perfect.
I have uvmapped it carefully each finger too, but usually it does not really worth it.