@Dan Stevens This is a separate field from the system "unsubscribe." Our instance was built before my time. How can I determine if the field is native or custom?
That's the culprit. Refer to Josh's list of fields that Marketo will use to suppress, regardless if a lead qualifies in the smart list of a smart campaign. Since this is more than likely a custom field - and certainly one that Marketo isn't looking at to prevent an email from being sent - you'll need to run a smart campaign to ensure any lead that has "opted-out" = TRUE, to change UNSUBSCRIBE to TRUE. And since it sounds like you're not using the out-of-the-box unsubscribe process with your emails, you'll need to make sure you opt-out process now includes the unsubscribe field as part of the process.