We don’t use Web Edition but we have a web app and what you’ll find is that as you grow there will always be users in the product, at all times of the day and night. So counting users won’t really help. A better plan, I think, is to pick a time when you know that there are unlikely to be many users, notify the users with a banner announcing your planned maintenance date and time in advance, and then just go offline at that time to do your update.
You can get the number of sessions which is the really important bit - each session may have many connections, but that is irrelevant. When the session count returns to 0 shutdown, update & restart.