Where do I start?
A lot depends on personal taste and water parameters. Livebearers (Mollies, Platies, Guppies etc.) would be great in hard, alkaline water. Most other species prefer neutral to softer water but many are adaptable to harder water. I prefer to see a limited number of species in larger groups rather than loads of seperate species of one or two specimens. i.e. a shoal of 20 Neons looks better than 2 fish of 10 seperate species.
As I say, it's down to personal taste. In a 20G small fish would be preferable. Some examples I can think of right now.
Upper water - Dwarf gouramis, Livebearers
Midwater - Small tetras i.e. neons, cardinals, glowlight, black neons.
Rasboras i.e. harlequins
Bottom - Corydorus species, various small Loaches
Algae eaters - Otos, Amano shrimp (livebeares too if they get hungry!)