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The main differences between using php mail() and wp_mail() for form submission are:

1. Functionality: The php mail() function is a basic email function that sends email message directly from the server to the recipient's email address. The wp_mail() function is a WordPress built-in function that provides more advanced email features for WordPress such as HTML formatting, attachments, and custom headers.

2. Ease of use: The php mail() function is easy to use but requires manual configuration of the SMTP server and email headers, whereas wp_mail() is easier to use and can be configured through WordPress settings or plugins.

3. Security: The php mail() function is more susceptible to spam and security issues as it does not provide any security features. Wp_mail(), on the other hand, provides built-in security features such as spam filtering and email authentication.

4. Compatibility: The php mail() function is a built-in function in PHP and can be used with any PHP application, including WordPress. However, wp_mail() is a WordPress-specific function and can only be used in WordPress applications.