If the 10g only has 2 neons and you intend to make it a total of 6 neons, yes you could further add 3 guppies to the tank. But do this over a couple of weeks so you can hopefully avoid a mini cycle ie. add 4 neons, wait 1-2+ weeks, add 3 guppies.
edit: erm, you might want to avoid opposite sex guppies, they will breed and quickly make your tank under filtered and potentially mess up the water quality