To show/list the users in a MySQL database, first log into your MySQL server as an administrative user using the mysql command line client, then run this MySQL query:
mysql> select host, user, password from mysql.user;
WP Migrate DB exports your database as a MySQL data dump (much like phpMyAdmin), does a find and replace on URLs and file paths, handles serialized data, then allows you to save it to your computer as an SQL file.