Actually the "Content Types" system is purely based on Field API.
c. Location - hasMany - Chapter ??
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So, you would like to add some input fields to your User information form? where you could select Location (selectbox) and multiple Chapters (check boxes).
User Form:
Location: [ Select Box ↓]
Chapter: [X] Chapter1
[_] Chapter2
[X] Chapter3
[_] Chapter4
I believe the best solution is create a Field to handle that kind of info.
For instance, Location & Chapers can be handled using Taxonomy Field, so you have 50% of the work done.
Field API may be tricky to work with, so a simpler solution is create a completely independent Module, with its own User table (Volunteers).
(QACMS modules are basically cakephp plugins)