tl;dr: No.
You can only change this on a subdomain basis, so either mail.domain.tld
goes through Cloudflare or not. So not, you can’t set that for specific ports. Also Cloudflare does, to my knowledge, not allow non-HTTP-traffic to bypass.
If you change the SMTP port to something else, nobody is able to send you emails as TCP/25 is always being used by othe rmailservers.