Any section of the configuration, such as <smtp>, can be "internalized," for example. stored in an external file.
Besides the operator file=on <appSettings>(which is available only for application settings :-() it is not an "additional" parameter - you just point your configuration system to an external file.
So you can get this in your app.config / web.config:
<system.net>
<mailSettings>
<smtp configSource="smtp.test.config" />
</mailSettings>
</system.net>
smtp.test.config:
<?xml version="1.0" encoding="utf-8" ?>
<smtp>
<network host="smtp.test.com" port="244" userName="test" password="secret" />
<specifiedPickupDirectory pickupDirectoryLocation="C:\temp\mails"/>
</smtp>
.NET 2.0 (, 1.x) , , <system.web>.
, , smtp.staging.config .., web.config.
, script, XML .
.NET 4 web.config, , , .