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Perhaps switch the download priority for Rimworld to 'High Priority', rather than 'Always keep this game up to date' or the option to only update the game when it is run - that should prioritise grabbing the workshop mods (and any game updates) before trying to download other games.
(While you're there, it may also be worth allowing Steam to download in the background while Rimworld is running - not related to your issue, but it's also not as though Rimworld requires bandwidth.)
After that's done, I would pick a (new) mod to subscribe to - for testing purposes - and once you've hit the button to subscribe, restart your computer.
Once Steam is back up, give it a sec to attempt the download and then check in-game to see if it shows up on the mod screen there, so you can enable it for use in a new playthrough.
If it hasn't, close the game and give Steam a little more time to do its thing.
Fix 1. Delete the Broken Mods.
Fix 2. Clear the Corrupt Download Cache.
Fix 3. Opt-out of Steam Beta Programs.
Fix 4. Switch to Big Picture Mode in Steam.
Fix 5. Change the Download Region.
Fix 6. Reinstall Steam
EDIT: Reinstall Rimworld maybe?
Might be worth saving up for a new physical drive, in any case.
Assuming you have more than one hard-disk in your computer:
Steam Library -> right-click on Rimworld -> Properties -> Local Files -> Move Install Folder. See if it will let you shift Rimworld over to another drive in your computer, perhaps.
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Edit: I realise the above is me making assumptions about the nature of the problem.
What was the solution, as you figured it? - The info you have may be useful to other people experiencing a similar issue.