Just because you're "head of processing" doesn't mean you shouldn't show any customer service. Furthermore, it's in regards to item processing and the obviously have a procedure for these situations as a "report" was filed and routed to a specific resource. I mean this is GOODWILL for crying out loud. Am I just naive to think that people who work at a place that takes donations would be so unhelpful when someone who has donated items accidentally gives away the wrong items?

It's definitely not the Goodwill's fault. It wouldn't hurt for them to be a bit more helpful though.