The whole point of "ordered pair" is that, unlike the set {a, b}, we distinguish between the two members. Writing (a,b)= {{a},{a,b}} just means that there are two members, a and b, and we distinguish between the two. Hurkyl's point about "the set {a, {a, b}} doesn't always have two elements" is that the "pair" (a,b) corresponds to the set {{a},{a,a}}. But since {a, a} is a set where we don't "double list" the same thing, {a,a} is the same as {a}. That means that {{a}, {a,a}}= {{a},{a}} which is exactly the same as {{a}}.
When talking about "ordered triples", we can think of (a,b,c) as the "ordered pair" ((a,b),c) where the first member is the ordered pair (a,b). That is the same as the set {{(a,b)}, {(a,b),c}}. But (a,b) is {{a},{a,b}} so {{(a,b)},{(a,b),c}}= {{{{a},{a,b}}},{{{a},{a,b}},c}}. Or we could write it as (a, (b,c))= {{a},{a,(b,c)}= {{a},{a,{b,{b,c}}}.
(That reminds me of the computer language "LISP"- "Lots of Insane, Silly Parentheses"!