Change to the Postfix configuration directory. Usually this is in /etc/postfix.
Open the sender_access file or create it if it doesn't exist.
Add the email address you want rejected on a new line in the file followed by REJECT.
Save the file.
Create the server_access database with the postmap command
Edit the main.cf file and add the following
Restart Postfix
Check your logs to make sure everything is good.