I purchase my DEF from Wall Mart, usually is 'Blue Def". It comes in 2.5 gallon jugs and comes with a spout you attach to the jug. You have to make sure the spout is screwed on tight, if not, they leak around the threads.
I always put paper towel around the fill port and drape some over the area where I'll be pouring to catch any drips. I also stuff paper towel in the overflow rubber funnel where the fill hole is.
I always start by tipping the 2.5 jug just enough the flexible spout hits the fill hole and shove it in. I let it drain and then begin to life the jug slowly letting it fill.
It's not rocket science, it's like filling gasoline into a gas tank with a gasoline can. I advise putting paper towel down over everything to catch drips. I never were gloves, and actually, I've never spilled or dripped any on my skin either. But I am careful, take my time, and don't let anything distract me when doing this either. DEF is very caustic. You don't want it spilled on anything. It will dry and turn kind like miniature white crystals. And even that is still very caustic. So clean up any spills immediately.