Add the labor table to the report 2 more times. YOu will get a warning saying it has already been added. Just hit OK to get passed that. The new Labor tables will have an alias name of Labor_1 and labor_2.
join labor_1.employee_num = Po.requestedby
join labor_2.employee_num =PO.modifiedby
I am going to guess that requestedby is required and modified is not required. If any field is not required you are going to have to make the join an outer join, otherwise it will omit all the records where there is no match (the nulls in the PO.modifiedby).
Drag and drop labor_1.employee_name to show the requestd by name and labor_2.employee_name to show the modifier name