hi,
yep, that gunk is mainly poo.

and uneaten food, decaying plant matter etc.
assuming that your pond is big enough to handle putting more fish in. you could get either or. but, heres a few things to keep in mind:
a pleco will eat
some of the junk on the bottom but, they are especially dependant on algae. and, if your neck of the woods gets pretty cold in the winter months, a pleco wouldnt fair too well.
a dojo will eat lots of junk off the bottom, but needs a varied diet as well as any fish. anything from worms to algae wafers to vegetables are great. dojos can also handle just about the same water temps as goldfish and koi and enjoy the same variety of foods. also, i dont think you would have to worry about them jumping out, a pond is actually an ideal setting for them as they can "walk" like mudskippers or catfish.
all in all, i would suggest a couple of dojos. they like to be in pairs/groups and together will make a huge difference on the amount of detritus on the bottom.
incidentely, how big is your pond? if its really big, you might be able to get a "handful" of dojos.
hope this helps!