You could do it like this (in a console app sample):

HtmlDocument doc = new HtmlDocument();
doc.Load(MyTestFile);

foreach(var node in doc.DocumentNode.SelectNodes("//div[@id='playerStats']/div/span"))
{
    Console.WriteLine(node.InnerText + " " + (node.NextSibling != null ? node.NextSibling.InnerText : null));
}

NextSibling is the next node after a given node with the same parent. It may not exist if the current node is the last child of a parent.

Note I have explicitely set element types to DIV for initial selection as it's better in terms of performance. (* matches any node).