Receiving Approver

I setup two employees with a Job and the Job has an approval level of 3.  I assigned one as my supervisor.

When I create the transfer, my supervisor is the only approver available  to select as the Releasing Approver which is as expected.

But when I pull up the LOV for the Releasing Approver, there are several choices, one being my supervisor, but the other employee is not there.  However I have all these other employees available in the LOV.  I can't figure out why these employees are in the LOV but not the employee I setup.  They all have the same job.  I am not even really sure how the Releasing Approver is suppose to work.....who should be in the LOV?