There are $\binom{10}{2}$ dominoes with two different numbers and $\binom{10}{1}$ with the same number on each square. Hence, the probability that a domino is a double is $$\frac{\dbinom{10}{1}}{\dbinom{10}{2} + \dbinom{10}{1}}$$ As for why your approach does not work, while you have counted each double once, you have counted each domino with two different numbers twice, once for each way you could pick one of those numbers as the first square.