I don't think there's anything I'd recommend individual episodes of, but there are some shows that shift tone after the first episode or season, where I'd advise skipping ahead. For example, the first season of Parks & Recreation is a much harder sell than season 2, imo; and I hated the pilot of Firefly (the way everyone treated Simon) and would have bounced hard off the show if we'd started with that.

For other shows I can think of with stand-out episodes, the episodes often work based on familiarity with the canon generally. Bojack Horseman's "Fish Out of Water" is one example.

(Of course, as soon as I post this, I'll think of half a dozen counter examples. ;-)