"PayPal Email" is the one that the money will be sent to, so will be shown. On PayPal this is the "business" attribute.
The only purpose of "PayPal Primary Account Email" in vBulletin is to verify the incoming payment in the IPN (payment notification) handler script. On PayPal this is the "receiver_email" attribute.
https://developer.paypal.com/docs/ip...dPDTVariables/
business Email address or account ID of the payment recipient (that is, the merchant). Equivalent to the values of receiver_email (if payment is sent to primary account) and business set in the Website Payment HTML.
receiver_email Primary email address of the payment recipient (that is, the merchant). If the payment is sent to a non-primary email address on your PayPal account, the receiver_email is still your primary email.
There's nothing to fix here, it works as intended. Somewhere on the PayPal site you should be able to modify the form that your users see.