I think, and I hope a zen-master jumps in and corrects or verifies, that there are two types of users in play here.
When you created the initial SQL database prior to installing ZC, you gave it a name, and then created a user and gave that user a name/password. I'm assuming that's the name you've got down there under DB_SERVER_USERNAME. Whenever you do something in the ZC that requires playing in the database, ZC goes to that line in the config to get the username/password to log in to the db.
All the other users are just admin users - people who have permission to log into the admin panel and do admin stuff. Those accounts are created from the admin panel - Tools > Admin Settings.
You can create 10 different administrators there, and they can all log in to the admin side and do admin stuff, but whichever one is logged in doesn't matter when it's time to write to the db - at that time ZC reads the config file, and logs in to the db as DB_SERVER_USERNAME.
So it doesn't matter how many admins you have, it shouldn't affect use. I still think it looks like your host server is unreliable. When it is down, have you tried seeing your storefront? Look at your webmaster account in Google/Bing and see if you're getting not-found errors of "unreachable". The settings in ZC are either off, or on. The password wouldn't work correctly one day and wrong the next.
I should add - if when you created your sql database, you also created multiple users, that too wouldn't have any effect on the equation. ZC logs in using the DB_SERVER_USERNAME and it could care less about who else you gave permission to.


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