Through pa30 check the employee's Groupings for Quotas by looking at IT2006. What does the Overview of that employee's IT2006 looks like?
Then, check the employee's Grouping for Absences by trying to create an IT2001 (no need to save it).
Next, check your configuration to make sure that it appies to the appropriate PSA and ESG Groupings, and go through the documentation in the Time Management Wiki.