Is it really the case that you need no CPU intervention for the external SPI flash write, for instance to set addresses or other command formatting? I suppose you could have steered the SPI flash into a streaming write mode. I don't disbelieve you, just curious.
You should be able to find a list of DMA request triggers for your particular chip in the reference manual. Off hand, I could imagine setting a timer (synchronized with your ADC) that generates a DMA request at an appropriate interval to do your second transfer. However, I wouldn't do this. As someone who has spent a lot of time stressing over low power sampling at his day job as well as some uncomfortable dreams, I would humbly suggest you are overthinking the importance of the DMA angle. I don't claim you are wrong, rather that the optimization is small, DMA is prickly, and there is usually better and lower hanging fruit.
IMO, the CPU waking up (from Sleep) for a handful of microseconds to do a little house keeping every now and then isn't going to move the power needle. Sleep is lower power than Run mode, but often only something like 50% less power. Check your datasheet. This is decent, but only applies maybe 0.01% of the time. Anything you can do to attack the other 99.99% is what will count. You should either be looking at trying to use Stop mode OR taking steps to cut your base power. Using Stop mode requires some strategizing and may not be reasonable beyond low rates. For the latter, look into disabling un-needed clocks/peripherals and cut everything else to the bone at least when Sleeping. IIRC, I have a STM32F103 based product which cuts HCLK as low 125 kHz when sleeping for this reason. More recent or advanced devices will have more tricks available to help you here, especially I'd assume on the L-series.