Copying my clock post? Impossible! Anyway,
Chapter one: using brute force.
Before you complain: I'm a physicist, this is how we do mathematics: by experiment. Ha!
We need cards! Inconveniently, Mathematica currently lacks built-in support for Kings. We therefore have to use a workaround: let's call the named cards by their numbers. A is 1, J is 11 etc. The deck of cards consists of the range of 1-13 four times, giving the deck array
deck = ConstantArray[Range[13], 4] // Flatten
{1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13}
Now let's setup the win/lose balance. While seemingly complicated in structure, this can be boiled down to a 2-tuple,
{win, lose} = {0, 0};
It is now time to ask the infinite monkeys to stop typing for a second and help us out play a couple of games, say ten million of them.
Do[picks = RandomSample[deck, 6];
If[Total@picks[[ ;; 2]] > Total@picks[[3 ;; 4]] \[And]
Total@picks[[ ;; 2]] > Total@picks[[5 ;;]],
++win,
++lose
];,
{10000000}
];
Run it! (Note: Monkeys don't seem to like being run in parallel.)
(Music entertains us while waiting)
Thanks guys, back to writing Shakespeare.
As for us, I've always been looking for an opportunity for making good use of BarChart3D.
Row@{"The probability of winning is ", 100 win/(win + lose) // N, " %."}
BarChart3D[{win, lose}]
The probability of winning is 30.8485 %.

Chapter two: using bruter force.
If the previous solution isn't accurate enough, we can use Mathematica's statistics sledge hammer, which happily kills all high school probability problems. In the following I'm assuming that the deck of cards is infinitely large (uniform distribution), which is close enough for all practical purposes.*
dist = DiscreteUniformDistribution[{1, 13}];
Probability[a + b > c + d \[And] a + b > e + f, Thread[{a, b, c, d, e, f} \[Distributed] dist]]
$\displaystyle\frac{8800}{28561}~(=30.8112\;\%)$
That's close enough to the experimental result, at least to astronomy standards.
*: Straight out lie to cover up that I haven't thought of how to determine the actual distribution