For players without a picture, create a folder (I called mine "mine") inside the data/graphics/pictures/players folder (I think that's the path.
Copy over a config.xml from somewhere else, and strip out the commands (leave the header stuff I guess). Put a line in there like this:
<record from="png name goes here" to="graphics/pictures/person/413915/portrait"/>
..basically just like the other .xml picture files in structure.
The photo should be of type .png, and the size should be 95x95, as well as having an opacity of 99%.
You'll have to load a new skin for changes to take effect. You can get the player ID numbers by choosing the "show unique IDs" from preferences.
For existing players, you'll need to find where they're entered in an .xml already, probably in their team's folder.
Hope that helps some.
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Changing pictures from one player to another, and adding new pictures ingame 
Linear Mode
