To this date, Proton Mail doesn’t support MTA-STS for custom domains. While DANE for SMTP is a much better solution to the same problem, MTA-STS exists for a reason: many providers are slow at adopting DNSSEC. DNSSEC is essential to enabling standards such as DANE or SSHFP. Notably, Gmail still does not support DANE but has supported MTA-STS for years.
Therefore, MTA-STS and DANE can complement each other, and you should ideally deploy both.