The answer to the main question is that the attachment directories section specifies a folder that gets copied to/near your export folder, so that, for example, if you replace 'DCIM' with '../Stuff' (no quotes, forward slashes even on windows), and there is a folder called 'Stuff' that is an 'aunt' of the folder your project file is in, that folder will be copied to your export directory, as sister to the project folder. The copying is dumb, anything in the folder will be copied with no regard to its being used in the project.
The relationships are a bit confusing in that a sister to the project .qgz will become a subfolder of the project's export folder, so to get a sister to the project's export folder, you need an 'aunt'.
The section says 'attachment directories' in the plural, but I have not yet found a syntax for specifying more than one that works (semicolons didn't seem to work, but testing this stuff is error-prone)
However, QField itself seems unable to use such directories: https://github.com/opengisch/QField/discussions/3726#discussioncomment-4333049