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Standard (individual) account only allows playback on one device at a time. You need to upgrade to Duo or Family for more than one.
To get around it I download various playlists in Spotify and then put my phone in Airplane mode so I can play them back whilst Mrs GB or MiniGB shout at Alexa to play whatever stuff they want to listen to.
(I don't care about quality audio. I listen to most music through Spotify and some of it out of a mono Amazon Echo Dot. Bite me.)
We are having Spotfiy wars in our house, after my wife decided to setup shop in our kitchen rather then the lovely hot desk I have in my office.
Was quite happy streaming Spotfiy through my desktop, now the wife's in the kitchen Spotify seems to prioritize playing it through the google hub thingy.