Creating stereo pairs is a semi-permanent process. Sonos lets you add and remove speakers from a playback group on the fly.
There’s also this nifty little app that makes grouping and ungrouping easier on iOS, especially when you’re using something like Plex/PlexAmp to control media.
My experience is that plexamp sees all individual Sonos speakers, or any that are currently grouped together on-the-fly within the Sonos app (I have to group speakers in Sonos app prior to casting).
Plexamp does not see Sonos Groups (completely separate from grouping on-the-fly) which are ‘permanent’ groups created in the Sonos app (as per screenshot)