Not that I'm aware of.
Any bank transfer that I've ever dealt with took X days to process... wasn't immediate.
Best of luck!
If you're talking about a wire transfer from a checking account at one bank to another bank you can get a transfer credited same day. But it seems that you want to do a transfer from a credit account to a bank, then redistribute that transfer to pay other credit cards. That's highly unlikely to happen since most transfers have to be batch processed overnight.
I'm curious though; two days ago you stated you had three credit cards and I'm sure none of them had a $20,000 credit limit. How are you proposing to transfer $20K?
Well, like I said you can initiate a wire transfer but its possible both sending and receiving bank will charge you for the service but the amount would be credited immediately by the receiving bank. That would allow you to make payments to your credit card without worrying about whether the funds are available in your bank account.
As far as I know Amex will only accept one payment through your online account during your first month of membership. But you can always call (800) 472-9297 to make a payment by telephone, or you can "push" a payment to Amex via ACH from an external bank.