I don't think there's any evidence to conclusively prove she was an Esper or related to any. It's possible, certainly. Her status as more of a legend than an actual person by the time PSIII takes place just means a lot of the details about her were never explored at all.
I would guess she probably would have been able to use the full range of techniques available in the game. At the very least, I'd expect her to have the healing and direct damage groups. When the game calls Laya a witch, that could just be a case of using the word as an insult to describe the unknown. I wouldn't take that as an indication of magic usage. Her pendant, the message in Mystoke, and the transport palaces do all hint at her possessing some ability beyond standard techniques, though. Those feats could have been accomplished using either technology or magic, I suppose.
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