Первый элемент массива имеет ключ 0, не 1.
var data = {
"lifeTimeStats": [{
"key": "Top 3",
"value": "1660"
},
{
"key": "Top 5s",
"value": "1471"
},
{
"key": "Top 3s",
"value": "606"
},
{
"key": "Top 6s",
"value": "738"
},
{
"key": "Top 12s",
"value": "1725"
},
{
"key": "Top 25s",
"value": "1989"
},
{
"key": "Score",
"value": "3,049,045"
}
]
};
var top_3 = data.lifeTimeStats[0].value;
var score = data.lifeTimeStats.pop().value;
alert(top_3 + ', ' + score);