In Total's guide, he makes the point that the value of the Plea heal is way lower than the value of the atonement that it applies. As such, I'm assuming that the PWS shield value (which is about 2.3 times the value of Plea heal) is not going to matter too much, and it's going to primarily depend on the mana cost of plea vs. mana cost of PWS. Plea costs 3456 mana at 5 atonements, whereas PWS costs 3,200.
Without doing the heavy math that would be required to estimate the value of atonement, I'm guessing that PWS becomes worth casting over Plea when you have 4 atonements up. If you have 3 or less, then you would be better off casting Plea (even if PWS is off CD).
Here's the quote: "TL;DR For Atonement application spells, PW:S will get its value anyway, and Plea/PWR are so small compared to the Atonement healing that we can discard the immediate healing value and only look at the spells as Atonement applying spells."
https://docs.google.com/document/d/1...UKd2672Ntg/pub