Simion, the encryption is to prevent any eye on it. If a program can decrypt it, it won't be secure. Think in your banking transactions over https.
I guess I'm not making myself clear here, so I'll rephrase the question: If Avast can decrypt and scan SSL emails, why can't Avast decrypt and scan SSL webpages?
Technically it doesn't decrypt your SSL email. The Mail Shield redirects your email traffic through its local host proxy, that is good for either sent email or received SSL email. But you must allow avast to handle the secure encrypted SSL connection.
So you using your email program want to check your email, the mail shield redirects that connection through its localhost proxy and the secure email comes back in to the localhost proxy at which point it is no longer encrypted and avast can scan it. If the email is clean then it is passed on to your email program/inbox, etc.
The same if you want to send email, that too gets redirected through the localhost proxy (at this point it isn't a secure encrypted connection) and avast can scan it. If it is clean then avast established the secure connection to transmit your email.
If you failed to uncheck the email accounts SSL requirement in your email program, then avast can't intercept and scan the encrypted traffic.