Solved. However, I can't explain what happened, so apologies for those that would hope to benefit from my experience. I manually closed the open instance of stunnel using Task Manager. I was then able to start the service. Upon subsequent reboots things work fine - this is despite the fact that multiple reboots didn't solve the issue. This is a standard instance of things solving themselves after posting for help - despite the fact that I had worked on it for hours prior.
If it reoccurs, I'll report back.