Hi ,
You can create an authoritative accept domain, then use the authoritative accept domain as an email address format to create an email address policy, and then apply the email address policy to specific users. Because there is only one default email address policy in Exchange by default, and the priority is the lowest, if you still want to keep the default primary SMTP address, then you can create an email address policy using the authoritative accepted domain that exists by default in Exchange and set the priority is higher than the email address policy created by the second domain.
But it should be noted that, according to my research and testing, you can successfully receive mail using the secondary SMTP address, but if you use the secondary SMTP to send mail, the recipient will still see the sender’s address as the primary SMTP address.
For more information: Create an Email Address Policy and Accepted domains
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