I don't understand how the settings module works... =P

Please see the wiki page dedicated to this topic, https://github.com/kyranf/robotarmyfactorio/wiki/Droid-Settings-Module

Read that, still not making sense to me, do I just choose a random item for each slot and set a value, and which slots correlate to which settings?

Sorry for the delay in responding. the slots don't matter, just choose a slot and put a signal in it - see the "virtual signals" category for the signal, and find the Robot Army setting related icon for the signal you want. Then, set the value for that signal. You will get a message print to the chat area when you successfully change the settings. If you choose an illogical/impossible value for a setting, then you will get warning messages spamming until you fix it.