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I've been doing some modeling work and started using PVA glue to go over areas that came out too rough or build up surfaces. I used it on a squig to make his teeth bigger and smoother because that is where green stuff is too soft. So far no problems. I was wondering if GW Liquid Green Stuff is just some type of PVA glue.

I have noticed that when I washed the model to prepare it for painting, the PVA parts turned white, but then they went back to clear. Are there any reasons I shouldn't use PVA glue instead of Liquid Green Stuff?

PVA and green stuff are made from different compounds. If you check the MSDS of these products, you will see.
The PVA turning white and then clear, is most likely caused by the water dissolving some of the glue.

As for reasons, I can't think of any at this stage.

Here he is. I put him in the toaster oven for 15 minutes on a low heat to dry the PVA glue, then primed with Tamiya Fine Surface Primer (which isn't as good as it used to be) to seal it. The muscles on the legs and body are all PVA.

You can't sand pva but I believe you have a thicker coat with pva (with lgs you need 2-4 coats) and it sticks maybe a little bit better.

If you use paper or cardboard then PVA is good for sealing it prior to painting. PVA once dry also cuts reasonably well and it's a lot cheaper.
I've never used liquid greenstuff but I assume it would flow better than PVA given that it's supposed to fill very fine holes and the like.