imagine a balloon floating in the air, and you give it a negative charge. This pumps more electrons into it (or onto its surafce). Giving it a positive charge (in relation to its suroundings) is done by removing existing negative electrons. Once all the electrons are gone, how could you possibly give it more "positive" charge? Whereas you can put as many electrons onto you want, limited only by the voltage of your charging source (and dielectric breakdown).
The analogy I'm thinking of is a sealed metal tank. as long as you have a strong enough compressor, you can pressurize the tank to whatever PSI you want (until it ruptures of course). But the opposite case, of sucking the air out to create a vacuum, you will never be able to create less than about -15 PSI (I'm talking Gauge pressure, not absolute pressure, which just like VOLTAGE is measured in relation to the surrounding "ground" conditions).
Does electric charge work the same way?