3rd party Certificates will not validate automatically in mail clients, you would have to add the CA certificate manually for each client.
The folder \externals\ca, I think is for validation purposes in ssl connections between 2 servers, not between client and server.
A much better solution is using good ssl certificates.
You can create a free ssl certificate (try https://www.startssl.com/) and then use it in hmailserver.
You just have to remember a trick that you only find in the forums (https://www.hmailserver.com/forum/viewtopic.php?f=6&t=24213 ). Because this certificate is signed by an intermediate authority, you have to concatenate your server certificate with the one from the intermediate authority. Using this concatenated pem file all your email clients will validate just fine this new SSL certificate and you dont have to use 3rd party certificates anymore. :)