I've had plenty of experience extracting lipids from biological samples for untargeted LC-MS analysis in HR mass spectrometers.
I've looked at the influence of solvent systems in liquid-liquid extraction protocols (Article A comparison of five lipid extraction solvent systems for li...
). Our work shows which solvent system is more suitable in case you're aiming to profile total lipids, but also shows which solvent system is most suitable for a particular lipid class. In case of sphingomyelin I suggest acidified Bligh & Dyer. But in case you're aiming for sphingolipids (sphingomyelin, ceramides, HexCer, LacCer, sulfatides and gangliosides) then my suggestion would be to choose between acidified Bligh & Dyer or extraction with t-methyl butyl ether (Matyash et al., 2008). This was achieved with small volumes (50uL). Also, the extraction protocol is detailed in the manuscript.
Pls beware that the extraction of classes of lipids from complex samples is always a compromise.