I just installed XAMPP, Apache is running, so is MySQL and Mercury.
In Dreamweaver I created a php file with a mail($to,$subject,$msg,\'From:\'.$email);
You would have to configure the mercury server bundled with xampp to actually deliver/relay the mails.
But I suggest you use something like SwiftMailer instead of php's mail() function.
edit: there is a third option. The mini-smtp-client built into php/win32 can't do authentication. Therefore you can't simply put SMTP=mail.gmail.com; smtp_port=25 in your php.ini. But you can set sendmail_path and point to an application that can relay the message to another smtp server (including authentication), e.g. fake sendmail.
(But I still suggest swiftmailer)