WordPress Users & WooCommerce Customers Import Export plugin facilitates the import and export of users effortlessly. To modify export column header name:
- Navigate to WebToffee Import Export (Pro)> Export.
- Follow the steps in How to export users to export your site’s user data.
- On reaching Step 4:
- select the required custom meta fields you want to export
- modify column header name
- re-arrange their order
Column header name modification
One can directly edit the column name and proceed to next step.

Example: On changing the column name: “ID” to “main_ID“, and the output will be:
Know more about Exporting.