If you mean eq2ui_loginscene.xml, you will have to manually add characters, servers and (optionally) passwords using Notepad. For the sake of privacy I don't manipulate this file, since account names and passwords are involved.
If you mean eq2ui_mainhud_shutdown.xml (the camp window) then you can add characters from in-game. Click the blue gem on the frame of the camp window to add up to 16 names/servers.
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