Baroness Zemo is actually Heinrich Zemo reborn in to a female body. She claims that this was all part of a ruse, but I wouldn't put it past Helmut Zemo to marry his father in a female body.
Rails are for normal people with normal heights. Superheroes/villains are usually taller and have more weight above the railing, leaving them prone to flip-flopping over it when enough force is applied.
Also see: sending someone over the top rope in wrestling.
I think he originally left it to Lana Lang, but she made the mistake of aiding Superman in some small capacity. Immediately the computer fired her and told her to leave the building or be shot.
If I recall correctly, Steve refused, not wanting to owe Red Skull anything. Red Skull only took more delight in saving Cap since he knew it would leave a bad taste in his mouth.
I remember that. The "war on drugs" was on so they couldn't have Captain America getting his power from the super soldier serum, a drug. So they wrote a story where Cap was exposed to "ice" which somehow fused to his serum laced blood, keeping him permanently high. Had to give him a blood transfusion to get it out of his system.
That was also the time where Kingpin fought Red Skull and utterly wrecked him, literally falling on top of the crimson cranium crook.
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