The difference is more important to me because I get catch-all mails for addresses on a domain that are no longer good (former employees) and they MAY have actually signed up to some of these things on purpose. This doesn't mean I won't both unsubscribe and also mark as spam completely useless e-mails from companies I don't care for. But I do notice that the RIDICULOUS volume of spam I get actually goes down sometimes when I do spend some time unsubscribing from what I find seems to be from legitimate companies, the frequently repeating contacts in the spam buckets. YMMV.
It's a pretty nifty interface that will automatically look up all relevant abuse contact emails for the ip ranges and let you file and register complaints with a single click.
1. You are not interested in their product or service (Obvious)
2. You read your mail, and it is not a throw-away box. (Non-Obvious)
Unsubscribe and your email address suddenly gets commercial value that it did not have before.
Then you're much more resilient than me :P
I used to do that but I thought, since they want to deliver their message, I'll deliver mine: "I don't want your unsolicited mail and I'll flag you without hesitation".
Apparently it works.