You need a GPG key to do this. If you do not have one yet, please refer to.
Select Edit ▸ Preferences ▸ Mail Accounts.
Select the account you want to use securely, then click Edit.
Click the Security tab.
Specify your key ID in the OpenPGP Key ID field.
Below the field you can choose whether to always sign outgoing messages when using this account, and other options.
Evolution requires that you know your key ID. If you do not remember it, start Passwords and Keys, go to GnuPG Keys, select the preferred GPG key, right-click on it, select Properties and copy the Key ID. Your key ID is an eight-character string with random numbers and letters.
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