When your accounts dosen't access all permissions for me i got solutions.
Goto your PermissionsEx folder then the permisssions.yml
For example:
users:
b14b92a8-87d8-3028-87c2-5ee9678c36b9:
permissions:
- /* <--- This will not work changed to '*'
options:
name: derp0987
Then save and goto console and /pex reload
Hoped it helps
Thanks,
tagxel