To switch the PayPal account that is linked to Gemini, you will first need to remove the linked PayPal account on the Payment Methods page. You can then add your new PayPal account.
If you would like to switch your PayPal payment instrument that is linked, you can do so by logging into your PayPal account, and changing your account settings to set your “Underlying Payment Method” for Gemini.
Please note, you are only allowed to link one PayPal account and payment instrument to Gemini at a time. PayPal is only available for customers who reside in the United States.