Hi Gabe,
Yeah. We never implemented that. I had hoped the developer who implemented the Spectral Library Explorer (View > Spectral Libraries) might get to it, but it just never happened and hasn't made it to the top of our priority list since that time.
https://skyline.ms/issues/home/issues/details.view?issueId=9
The current implementation allows you to prioritize libraries by their ordering in the list you see in the Peptide Settings - Library tab, but there is no UI for manual assignment that goes against that priority order.
I assume you are casting your vote for our making the time to implement that more explicit assignment UI. I have reopened the issue to give it that opportunity.
Thanks for posting your feedback to the Skyline support board.
--Brendan