Could this be managed?
A TWF build with a two bladed sword and a throwing buckler?
If so how would you build it?
Well, the general rule is that each limb can only have one attack (or set of attacks with iteratives). Are you saying you would throw the shield and then use the double weapon? Sorry, but you can't change stance mid attack.
Of course if you somehow have extra arms then no problem. A couple of levels of alchemist would help. The vestigial arm can give you enough to pull this off. For cosmetic concerns, maybe have two arms on one side to pull off the two bladed swords, and a shield on the other side.
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Why? You can be holding the 2 bladed sword in 1 hand. What sort of action is it to put your hand on a sword? Certainly not a move action.
I've never looked into throwing a shield so I have no idea it's a standard action, but I've seen (but nor read) enough "Captain America" threads to presume that there must be a way to throw a shield in similar fashion to throwing an axe or dagger.
But, like I said I've never explored this so there is a very good chance I'm wrong.
Well, as I said, you can't change the way you hold your weapon during the attack. If you make more than one attack, it typically has to be a full attack.
These rules are based more on preventing you from abusing them like the example this thread is about. For another example, if we didn't use rules like this, someone could wield a greatsword for a full iterative, then drop it and attack with two claw attacks in the same round. While that is slightly different than simply supporting the dual bladed sword, the arm would still be making more than one kind attack in the same round.