Задачка, конечно, не для MySQL, но решение есть:
SELECT u.*, t2.date FROM users u LEFT JOIN (
SELECT @rn := IF(t1.prevdate IS NULL, 1, @rn + 1) rn, t1.id, t1.user_id, t1.date FROM (
SELECT o.id, o.user_id, o.date, o2.date prevdate
FROM orders o
LEFT JOIN orders o2 ON o2.user_id = o.user_id AND o2.date < o.date
LEFT JOIN orders o3 ON o3.user_id = o.user_id AND o3.date > o2.date AND o3.date < o.date
WHERE o3.id IS NULL ORDER BY o.user_id, o.date
) t1, (SELECT @rn := 0) sg
) t2 ON t2.user_id = u.id AND t2.rn = 2