In any other industry, your PTO is paid out in actual hours accrued which is usually dependent upon hours worked. In this case OT does not apply.
If you've set yourself up with an agreement that gives "one week" or "5 days" off (or however many days it is) rather than hours then yes, you should pay the regular weekly rate.
OP, your scenario is confusing, can you clarify how many hours the nanny worked in her week and what your PTO agreement is?