What you described is absolutely normal. The number of real stat points your Pokemon gains from EVs depends on its level. What you read about four EVs giving one stat point is only true at level 100. At lower levels, EVs do not contribute as much to your Pokemon's stat total (strictly speaking; the proportions are the same).
At level 31, your Pokemon needs approximately 13 EVs to gain an extra stat point (subject to rounding and other factors). The reason that you didn't see any stat gains after using 10 Vitamins (even though you should have gotten at least seven points) is that stat recalculation only occurs upon level up in Gen 4. If you level up your Pokemon, then it will gain at least seven points in the stat you used 100 EVs on.
You do not need to worry about the timing of when you used your EVs. Your Pokemon is not disadvantaged by the fact you used Vitamins at level 31 instead of level 100. Your Pokemon's stats are recalculated every time it levels up, which will keep it caught up. So, yes, your Pokemon will still have high stats when it gets to a high level (with Rare Candy or otherwise).