Choose a default email address to send mail from on iCloud.com

If you create an email alias or create an email address with a custom domain, you can select one to be the default email address you send mail from.

You can also select which email addresses you want to be able to send mail from in addition to the default address. The selected addresses appear in the From pop-up menu when you create a new email. See Write and send email.

Go to icloud.com/mail, then sign in to your Apple Account (if necessary).
Select at the top of the Mailboxes list, then choose Settings.
In Account settings, select the email address below Send From.
Select all the addresses you want to use to send mail in iCloud Mail.
Select the Default Send Address pop-up menu, then choose an option.
Select Save.

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iCloud User Guide

Choose a default email address to send mail from on iCloud.com