First off, you really should have read everything about the card, fees, and the entire process before signing up. It’s a bank, after all.
That being said, the card is, of course, not free. You won’t have to pay for shipping or anything else right now, but Payoneer has annual or monthly fee that you pay when you have money on your account. This doesn’t mean that you can use your card but get out of paying by not withdrawing money to Payoneer for a period of time, because the funds will be automatically taken from your balance as soon as you have enough money. Fees depend on how you registered, so you’ll need to check that on your own.
As it must have said on the website while you were registering, the waiting period for the review is a few days, and for the card around two weeks. I’m not sure the process of approval is entirely automatic, so you might have to wait until Tuesday because of the weekend and the holiday in the U.S. Don’t order a second card until you hear from Payoneer because you might end up having two. If you don’t get the email in say a week or so, contact them and check before doing anything else.
I strongly suggest you go though Payoneer’s website and read everything regarding fees, rules and regulations, how you can use the card, etc.