The available shipping and payment methods are configured at the user group level. By default, all delivery and payment methods available on the website are enabled for all groups.
To set up restrictions:
Go to the section Customers → Customer groups.
Click the desired group to edit the settings.
In the Delivery and Payment blocks, uncheck the boxes of the methods that should not be available to this group of customers.
Click Save.
Please note: Delivery or payment options that are disabled in the section Settings → Shipping methods and carriers/Payment methods will not be available to all customer groups.