the spike chain grab can be preformed one of 2 ways.
Method 1: (note: this is how I do them other people may do them differently/better) you will be spiking them out of a down throw. first press down, then, as quickly as possible, do a half circle into the up position(note: the half circle should be in the direction you are facing. i.e. if you are facing right your half circle should input the directions going to the right) this , if tap jump is on, will cause Nana to jump, then do a quarter circle to the right and hit A. You must do this very fast on lighter characters.
Method 2: you will be spiking them from a forward throw. Hit jump then quickly hit forward and A.
For the Hobble a.k.a. the footstool chain grab press and hold forward while you spam the jump button. Once you see Nana Toadstool the opponent begin spamming the B button. Once the block hits them wait about a half a second (for invinciblility frames to end) and then re-grab.
For Z-grabbing a.k.a. the infinite chain grab the best one to use is Hylian's method while substituting the down throw for a forward throw. It does 2 more damage and is less varied by character weights. This is the most difficult chain-grab as its timing is very dependent on the weight of your opponent. I should be something like this. Tilt control stick forward, this causes nana to walk forward slightly as popo throws. Have Nana grab them. Then tilt the control stick back toward you so that Nana throws toward you then have popo grab. Rinse and repeat.
Sorry if this all looks confusing, but I hope it helps