OK, the final solution is for blocks like poetry/song, where alignment of the character is more important, to simply remove ALL alpha characters from the alignment, and simply leave the punctuation (on the left, anyway).
After some fiddling, I found out the "rationale" behind the wonky column of Ws. The first line's quotation marks are indeed treated as 100% left, as in not optically aligned. The side-effect of this is that the very next character, the first W, is aligned perfectly with the assigned indent. The visual disparity comes from the following lines also having W, which ARE being affected by Optical Alignment.
In edge cases like these, it'd be convenient to have a further option - "if first glyph has 100% adjustment, apply optical adjustment to following glyph?" Food for thought.