Try more delays?
Look at what franman will do to abuse Cervy's command throw. He knows there's no reason to duck against Cervy that close, so he just crouches and waits for you to stand up or block, then tries to hit you with the command throw. You could work delays in with Mina to get the same effect.
66a is safe, but doesn't knockdown or do much damage, that's the problem it has. But if they want to block it, let them. Pogo is unsafe, but does good damage. Throws are just slow enough that some people will try and duck them on reaction. If you can hit enough 66as they'll eventually want to stop getting hit by them, and if you can predict a crouch pogo instead, since it's got way more damage and range.
It also depends on where you're trying to use throws. Is it an ambiguous situation up close where you don't think you have enough +frames to get a guaranteed punish with 6b+k or whatever? Because then they'll be expecting a throw, and you're more likely to hit them with pogo or 66a. If you're just running up and throwing many people will spot that as well, and if you catch them crouching you can hit them before they realize you're not going to throw. You just have to time it right after reading them.
Another approach is to start with lows and work your way to the throws. First convince them that they need to crouch, then use 66a to convince them they need to stand. That way they're looking for a low animation to crouch and block, instead of a throw animation to crouch under. It gets harder and harder to watch for multiple animations at the same time, and if the lows are annoying enough (4a, 1k, 3a+b are alright for that), then they'll be looking for them more.
Pogo and throw mixups are too slow to abuse, but if you use them at the right time they work. Try pressuring their soul gauge a bit first; when people see it get red, or start to flash, they tend to make riskier defensive decisions.