There are a couple of things you can check if an employee (new or existing) does not show PTO Accrual:
1) Does this employee have a "primary department" set?
How to set a primary department. Please follow this link - http://support.myhourdoc.com/entries/20946948-how-to-set-a-primary-department
2) Is the employee marked as DoA eligible (under employment tab)?
Eligible to earn days off. Please follow this link - http://support.myhourdoc.com/entries/20924341-eligible-to-earn-days-off
3) Is the employee eligible as per the day off accrual settings (i.e. has he been hired long enough to start accruing?)
NOTE: A typical sign that employees are not setup correctly is when the Day Off Accrual report shows "N/A" across the row.