The madExcept settings are stored in a file named "yourProjectName.mes". If such a file doesn't exist, default settings are used instead. Which is not probable in this case, though, because by default SMTP mailing is not enabled.
You can change all the settings at runtime, if you like. See more details here:http://help.madshi.net/MESettings.htm
For example, you could do "with MESettings() do begin SmtpServer := '...'; [...] end;".