I remember theres a way to specify certain parameter overrides per-recipient, but is there a way to override smtpd_client_message_rate_limit per-client IP address? Right now smtpd_client_message_rate_limit is set in main.cf
Is smtpd_client_connection_count_limit what you are looking for? http://www.postfix.org/postconf.5.html#smtpd_client_connection_count_limit