When paying a credit card can I first apply payment to the balance (from cash adv) with the higher interest?

Since I am being charged more for the portion of my credit bill from a cash advance, when I make a payment I would like to allocate my payments to pay off the higher interest portion of my credit card balance first. Is that possible.

Sadly it's not. That's how credit cards are tricky. Your best bet would be to pay that card off as quickly as possible and then not use your credit cards for cash advances. If you have the ability to balance transfer to another card, that would get your balance at a lower interest.