If the remote server is using SNI (that is, sharing multiple SSL hosts on a single IP address) you will need to send the correct hostname in order to get the right certificate.
openssl s_client -showcerts -servername www.example.com -connect www.example.com:443 </dev/null
If the remote server is not using SNI, then you can skip -servername
parameter:
openssl s_client -showcerts -connect www.example.com:443 </dev/null
To view the full details of a site's cert you can use this chain of commands as well:
$ echo | \
openssl s_client -servername www.example.com -connect www.example.com:443 2>/dev/null | \
openssl x509 -text