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Early on I say witch has an advantage. She gets a hex at level 1, so can take extra hex at level 1 and have the core hexes (Evil Eye, Cackle, Misfortune) by level 2, where the shaman is getting his first hex. Additionally, wandering hex cannot be used to pick up a debuff, so without feat expenditure it takes a lot longer for the shaman to get up and running.
Shaman is tankier though, and since you need to be in 30 feet for most the hexes that is very nice. Also, the shamans evil eye is not mind effecting (which may be a mistake) which is a giant boon IMO.
By the mid levels they are pretty much tied, but I think the witch pulls ahead again in the later levels with Major and Grand hexes. I think both classes do the job fine though and it depends what your looking for whats the better option.
Edit: And there is another thread that pointed out, it appears RAW the shaman can't pick extra hex feat to take any hexes except those granted by his wandering spirit. Hopefully this is an oversight and will be FAQ'd, but if not then the shaman will take a long time to get up and running.