Currently global settings give you an option of setting an account to be used by default for every new message (the same account no matter which account is selected) or using the account of the last message sent. This account determines the "From" address, signature, and sent-message folder. (Identities can affect that too.)
Neither of those work for me.
It would seem more intuitive to use the account for the folder that is currently selected in the account list, or being viewed in the message list. That could be an additional option in the global settings, or even better, a new setting for each account. If the current folder selected or viewed is the SmartInBox, then the global setting could work like it does now.
I have different mail accounts for different organizations, jobs, and clients. It can cause problems to get them mixed up. I use Aqua Mail mainly because it handles multiple accounts and identities. But it's too easy to assume it will use the account of the messages being viewed, and forget to change it to the account or identity I intend. If this request cannot be satisfied, then it would be better to not default the account at all, and force me to select an account or identity for every new message.
This does not apply to replies - they should continue to use the account or identity of the original message.