I believe I have discovered the issue. There is a toggle called "Use To: address for replies." When this is enabled, the Default From Address can be overwritten when an SMTP account or an Alias is present and in the To address field of an email being replied to. You can find the setting under: Settings > Account > WebmailI was able to replicate when I added an additional SMTP account and EWS account. It seems SmarterMail's logic for selecting the From address when the “Use To: address for replies” option is enabled is consistent but is somehow reliant on some other factor than the To: address like it should. This lead me to believe I was not replicating the issue.
Please understand that I'm unfortunately unable to provide a timeline of when this will be addressed by the development team, as it may take them some time to research and review the problem, then implement a solution. However, we will provide you periodic updates on the progression of this resolution. We also ask that you keep an eye on the release notes of future builds for information relating to this functionality.
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