Can you take additional amounts for Federal and/or State taxes?

Yes, if the employee has indicated on their W-4 that they wish to have additional taxes withheld, you will enter that amount in Employee Management-Employee Pay-Tax Information.

Where do I go to add in an additional amount for State withholding?

To increase an employee’s state withholding, go to Employee Management-Employee Pay-Tax Information.  Enter the additional withholding in the additional field.  Adjust the drop down to either Amount or Percent based on the employee instructions.