Sentience is basic self-awareness, knowledge that there is a "me" who is distinct from the rest of the world. Arguably, most avians and mammals, and possibly some reptiles and archosaurs, are this smart.
Sapience is awareness of awareness, the recursive ability to think about thinking and thus to choose to think, to consciously reason as opposed to merely thinking in response to one's environment. Arguably, numerous avians and mammals, including but not limited to many corvids (crows etc.), psittacines (parrots etc.), primates (apes, etc.), proboscideans (elephants), ceteceans (dolphins, whales) are sapient, though few of these to the degree of humanity. This is hinted at by various kinds of animal cognitive testing and observed behaviors in the wild.
If we encountered a species which had a fully-syntactical language; a complex economy including contracts and long-distance trade; built houses, cities, steam engines, railroads, wagons, farms and factories and mines; and created fine arts and literature, only the most arrogant sort of humanocentrism (*) would enable us to argue they were non-sapient. So the Ponies are most definitely sapient, and probably around as intelligent as human beings.
The Mane Six, of course, would range in human terms from high normal (Rainbow Dash) to supergenius (Twilight Sparkle) cognitive levels. The combination of intelligence and millennial experience possessed by entities such as Celestia and Luna would probably be beyond our ability to measure, since all the human analogs would be with mythical beings such as Athena or Artemis.
So yes. They're sapient.
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(*) Which, unortunately, humans frequently display in regards to non-humans.