How to change primary domain name of cPanel account:
You can change the primary domain name from the WHM. For that,
Login to the WHM as root user
Go to the location,
WHM -> Account functions -> Modify an account
Now you will be able to change the domain name of the account. Also here you just need to replace the domain name field with the domain name that you need to set. Here you can also change the username, but it is not recommended because of the username is used for configuration files as well as databases.
Once you have changed the domain name here in WHM it will automatically make the changes on cPanel as well.
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