I'm a Jr. sysadmin at a medium sized software company. Whenever I document workflows for our users, I have two colleagues of mine who have no connection to IT work through them and add the small gotchas they asked me to the docs.
It saved me a whole bunch of headaches for when other users get enrolled in these workflows.
I've been doing some cal/QC functions recently after years not touching it. Since I last did it I've forgotten some of the knowledge that is just assumed. The answers to my questions are documented, but not in a places that is accessible from the production side and has lived as community knowledge in production. I've been making a list and updating the documents to fill in some gaps.
Unfortunately some of the production people aren't comfortable enough pushing for changes in the documentation so some of my job now is to ask what they've noted and get it added.