Ok, I've solved this after so long... I'll write down how for those who're facing the same.
First, as a CWP Pro user, I've opened a ticket on the issue. Unfortunately, nothing came out of it (they've sent me to my host, don't ask me why). So... after self learning and investigating, and many fails and errors, here's what saved the issue:
1. I've found accidentally that my /etc/hosts file was totally wrong. Here's how it was:
# The following lines are desirable for IPv4 capable hosts
127.0.0.1 hostname.domain.com.domain.com.domain.com.domain.com.domain.com.domain.com hostname.domain.com.domain.com.domain.com.domain.com.domain.com.domain.com
127.0.0.1 localhost.localdomain localhost
127.0.0.1 localhost4.localdomain4 localhost4
# The following lines are desirable for IPv6 capable hosts
::1 hostname.domain.com.domain.com.domain.com.domain.com.domain.com.domain.com hostname.domain.com.domain.com.domain.com.domain.com.domain.com.domain.com
::1 localhost.localdomain localhost
::1 localhost6.localdomain6 localhost6
127.0.0.1 hostname.domain.com.domain.com.domain.com.domain.com.domain.com.domain.com
127.0.0.1 autoreply.hostname.domain.com.domain.com.domain.com.domain.com.domain.com.domain.com
xxx.69.16.xxx hostname.domain.com.domain.com.domain.com.domain.com.domain.com
Here's how it is now, fixed:
# IPv4
127.0.0.1 localhost localhost.localdomain localhost4 localhost4.localdomain4
# IPv6
::1 localhost localhost.localdomain localhost6 localhost6.localdomain6
# put your IP address and your hostname and aliases below
xxx.69.16.xxx hostname.domain.com hostname
Ok. that removed the first 2 lines in my initial error log. But left me with the SSL error:warning: TLS library problem: 5488:error:14094418:SSL routines:ssl3_read_bytes:tlsv1 alert unknown ca:s3_pkt.c:1493:SSL alert number 48:
2. After looking for so long all around, I knew something in my configuration is not pointing to the correct CA SSL certification but didn't really know how to fix it with the correct one. Then I found
paldig's post here, which saved me.
Edit /etc/postifx/master.cf and replace these:
smtpd_tls_CAfile = /etc/pki/tls/certs/ca-bundle.crt
smtp_tls_CAfile = /etc/pki/tls/certs/ca-bundle.crt
With this:
smtpd_tls_CAfile = /etc/pki/tls/certs/hostname.domain.com.bundle
smtp_tls_CAfile = /etc/pki/tls/certs/hostname.domain.com.bundle
And viola! issue solved!