I tell my friends and family to never use "unsubscribe" links unless they have a close relationship with the sender. How folks decided directing people to click links in spam email is beyond me.
There's no "Unsubscribe and report as spam", just "unsubscribe" and "report spam".
If it's a regular email that you vindicatively want to classify as spam, do that and don't unsubscribe. It will go directly to your spam folder in the future, and it will hurt a tiny bit their standing with Google.