Your problem is a blocked tank vent....and no, the vented loop won't break a vacuum in the tank. All tanks vents--fuel, water and waste--have two primary functions: to provide an escape for air displaced by incoming contents and to provide a source of air to replace contents as they're drawn out. When a holding tank vent becomes blocked, continuing to flush the toilet pressurizes the tank...which explains why waste gushed out of the pumpout fitting when you opened the cap. When no air can enter the tank to replace contents as they're pulled out, the pump--pumpout or overboard discharge pump--will pull a vacuum that prevents more than a small amount from being pulled out....which explains why neither pumpout nor your gravity drain could empty the tank. Clearing the vent will solve your problem. Do NOT use the toilet again until you have cleared it.
The two most common locations for a vent blockage are the vent thru-hull--which on a Catalina is only a slit in a rail stanchion unless a PO has relocated it to a thru-hull-- and the other end of the vent line--that end of the hose and the vent fitting on the tank. Start by scraping out the slit in the rail stanchion or the thru-hull if there is one...use a screwdriver blade or whatever works. Then remove the vent line from the tank (warming the hose a bit with a blow dryer will make it easier to get off)...now that you've relieved the pressure by opening the pumpout cap, it should be safe to do so without spewing waste all over that area, but I'd open the cap again before you remove the hose just to be on the safe side. Scrape out the end of the hose and the tank fitting. Put em back together and you should be good to pumpout.
There's an ongoing discussion about this in the Plumbing and Sanitation forum and in at least one of the Catalina forums now...you might want to check them out. And the archives of the Plumbing and Sanitation and the Ask All Sailors forum are full of blocked vent threads. Spending a little time reading them will help you prevent a lot of sanitation system problems.