That pop-up address selection list is part of auto-complete. According to MozillaZine:
Auto complete uses both the main and additional email address in a
contact. It alphabetically sorts entries in the pop-up. However, if
you have sent a message to a contact three or more times auto-complete
will sort the entries alphabetically, but it will list the main
address before the additional email address for that contact.
So one solution is to make the preferred address the main one. I've tested this on my own system, and that works.
You can also store separate contacts for a person, and manipulate the names to control the sequence. The first address in the pop-up list is pre-populated in the address window, and it is based on the characters you have already entered. So, when you type the first letter, the pop-up list will contain a sorted list of names starting with that letter. If your boss's name is not the first name in the list, a different name will be pre-populated until you enter enough characters.
You can manipulate the alphabetical presentation sequence somewhat by how you store the name entries (both the one you want and others that may precede it in the list). For example, Robert
vs. Bob
, or you can prefix the name with the company name or a descriptor, like Home
or Work
, or even add a number (Bob Smith2).
MozillaZine does list an addin, MoreFunctionsForAddressBook, that claims to include the ability to change the address presentation order. I haven't used it and don't know whether it has been maintained and is compatible with recent releases of Thunderbird. Their certificate expired a few months ago and I had to override Firefox's security warning to view their website. This addin isn't currently listed in the available addins list from within Thunderbird, and wasn't found when I searched the addin list by name, so that's not promising (but you can download it directly from the publisher at the bottom of the linked page).