A couple of points:
1. There is no way to remove a domain from an existing certificate. Changing a certificate in any way always results in a new issuance. That's just how certificates work, nothing specific to Let's Encrypt. Certificate issuance cannot be scaled to infinity, so the same limit has to apply here (otherwise anyone could just bypass the rate limit by adding and removing subdomains and launch a DoS that way).
2. The relevant rate limit here would be 20 per week, not 5. (5 is for completely identical domain sets, i.e. duplicates)
3. Do you revoke the certificate after reissuing it without the subdomain (i.e. because it's a delegated domain and your user explicitly wants to remove trust)? If not, you might as well keep it around until your next renewal of that particular certificate and remove it at that point.