There are times when you cannot change the account when making payment by PayPal. Payments will be made with your default payment method unless you select a preferred payment method.
After making the payment, login to PayPal, click on "Profile" (ignore the drop down menu), click "My money" on the left, click "update" in the "My preapproved payments" section.
You will see the transaction there and click on the "Merchant" link of the transaction, click "Change" of the "Backup Funding Source" in "Funding Source" to select your preferred payment method.