No, custom fields are for issues only.
The closest you can get off-the-shelf is that users can have properties associated with them, but only admins can set them, and you need a plugin to expose them outside the user profile/admin screen.
Ok, I'm a bit fuzzy on one part - I don't know if OnDemand admins can set user properties. It sounds like you've found it, and you can though :-)
But for the rest, there are two parts:
Yes, you are spot on about adding a key and value. Only admins can add them, only admins can view them, and on that basis, frankly, they're useless. Other people need to see the, but its admin-only. Pretty useless in general. (But add one anyway, for this test)
Now, the Jira toolkit kicks in - add a custom field of "user property field" as usual. Then set the default value to "reporter:key" or "assignee:key". Next time you go to issues that have it on-screen, you'll see whatever <key> you set, based on who the reporter or assignee is.
Unfortunately, it's still not searchable.
I don't know Tempo well enough to give you a decent answer
Property fields on users are notoriously difficult to use - there simply isn't much functionality around them. Such as searching or displaying - the view field in the toolkit sort of solves the problem, but you then have the odd situation where you are looking at a user property via an issue, and the data is not actually directly related to the issue.
If you copy these things with post functions, you'll be making a fundamental change to the information you're manipulating - once you've copied it, the data will belong to the issue. If you change the user associated with it, or you change the property on that user, then your copied data on the issue won't match. That might well be what you want (I've got a function here that says "capture the group(s) of the person doing X to the issue - if they change jobs, and hence groups, we do NOT want to change the issues because we need to know in what capacity they did it in, not what their current role is). But you need to think all of this through.,
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