User Sync not syncing additional capabilities

- User Sync not syncing additional User roles that are added with User Roles editor plugin.

- Custom user roles, created with User Roles editor are not synching

Also please advise:
- What and how are syncs triggered? Obviously, re-syncing manually will be a pain.
- Why might my custom user roles not be picked up, as the default wp user roles work okay?

Cheers