I use my personal Gmail domain account to consolidate four (4) other accounts, two (2) of them work accounts.

I know there is a way to select the "From" address when composing a new mail, but how do I make Gmail ask or prompt me so I don't ever accidentally leave the wrong address set?

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No, but I believe when you reply to a message it sets the To: field accordingly.

This is done when the
"Reply from the same address the message was sent to"
is checked in Settings > Accounts and Import

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