The first rotates first theta degrees about the axis (0,0,1) and then theta degrees about the axis (1,0,0). The second rotates only once, theta degrees about the axis (1,0,1). I think it’s pretty hard to explain in words why it’s different, so I suggest you write an application that performes these two rotations on two cubes next to each other and see for yourself.
It is possible to emulate two rotations (if not all possible combinations, at least most of them) with a single rotation. Search the web for euler angles to axis angle conversions and see what you can find. I don’t know of anything myself, sorry.
And matrix multiplications are not comutative, meaning order of multiplication is important. AB is not the same as BA.