Exceptional service is rare, so when I receive it I usually try to let their manager/store owner know. If large co., then I let manager know but also email corporate. In my email I describe the exceptional service I received and I ask that the employee be recognized for it.
I just did this yesterday for a banker at a Wells Fargo branch. He went out of his way and helped me out with a somewhat complicated matter. I asked him how I can help him get recognized for his exceptional service. He was thrilled.
On the spot, I sent an email to Wells Fargo corporate and also talked to his manager asking her to make sure he gets recognized.

Corporate replied via email, "I've forwarded your comments to the appropriate manager. They'll recognize [] for providing you with excellent service."
It took me just a few minutes to do, but has potential to really help out a guy who really deserves it.

I've done this many times over the years and it's become a habit when I receive truly exceptional and out-of-the-ordinary service.
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