You won't be able to add it to the watch list but you can pretty much achieve the same thing by modifying the notification schemes to include the custom field where ever the watchers are used. Will that help?
"Adding the user picker custom field to the notification scheme is probably the easiest way to do it and does achive what I was thinking. The only downside is that when assigning a user into the custom field that user is not notified. Some other event would have to happen before they would be notified. Does that make sense? The idea was actually to have a second field that maintained who the QA person for the issue was. I realize that technically the issue should be assigned to that person during the QA part of my workflow but in this case I want the developer to always have the assigned ticket."
Actually I think the Issue Updated Event would take care of this.
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