Short answer
Yes, but mostly at each other — over food, space or unwanted mating attempts. Well-handled alpacas rarely spit at people.
Alpaca spit is a mix of saliva, air and green fore-stomach contents. It is mainly a social signal: an alpaca pins its ears back, raises its head and warns before spitting.
People usually get hit when they stand between two arguing alpacas at feeding time. Pregnant females also spit at males to reject them (the 'spit-off' used as a pregnancy test). Hand-raised or poorly socialized alpacas may spit at handlers.
If you do get spat on, the smell washes out with soap and water. To avoid it, spread out feeders and don't step between quarreling animals.
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