You can probably achieve the ordering you desire by using the Custom Entry Order extension. If I understand correctly, to achieve what you want you would give every entry within the category the same order value. Using the order values you can determine which categories are higher priority. So, based in your example, you would assign an order value of
1 to the entries assigned to High School Teachers and an order value of
2 to the entries assigned to the
Math category. The result would be all entries within High School Teachers to be listed first in alphabetical order followed by all entries within the Match category in alphabetical order.
Hope that make sense and helps!