Skrill takes awhile to set up (took me 3wks. before they'd gone through the entire procedure, ie. verifying address it took them over 2wks. to get the letter to me (with code in it to verify with)).
My suggestion would be to > deposit with MasterCard
GiftCard (if you want to play instantly). Then start working on the Skrill process. Then make another small deposit with Skrill so that you can withdrawl via Skrill.
imo this is your best bet in order to play right away & then be setup with the easiest method for later on.