The highest level spell I could find that uses a melee spell attack to deal damage is Mordenkainen's Sword (level 7). The relevant part of the spell reads:
When the sword appears, you make a melee spell attack against a target of your choice within 5 feet of the sword. On a hit. the target takes 3d10 force damage. Until the spell ends, you can use a bonus action on each of your turns to move the sword up to 20 feet to a spot you can see and repeat this attack against the same target or a different one.
However, it's worth noting that Plane Shift (level 7) requires a spell attack and a save to let you banish an enemy, which is equivalent to killing them most of the time:
You can use this spell to banish an unwilling creature to another plane. Choose a creature within your reach and make a melee spell Attack against it. On a hit, the creature must make a Charisma saving throw. If the creature fails the save, it is transported to a random location on the plane of existence you specify.
Otherwise, for a wizard, there aren't really spells that start at high level that require an attack roll.
Yes, you can target multiple enemies
The action you take is not dependent on the trigger you set.
First, you decide what perceivable circumstance will trigger your reaction. Then, you chose the action you will take in response to that trigger, or you choose to move up to your speed in response to it.
For example, you could set a trigger of "When an orc comes into view" and set your action to be "heal my ally with this spell".
The only thing you need to make sure is that your action wording does not exclude targeting multiple things. For example a readied action of "target that one orc with eldritch blast" would only allow you to target one orc technically. Whereas a readied action wording of "I hit as many orcs as possible with eldritch blast" would obviously allow you to do target multiple.
Note that you don't even have to specify targets of your spell before you release it. All you have to do is cast the spell with the Ready action and set a trigger for its release. Upon the trigger being met, you can then choose to release the spell and it is at that point that you would choose the target(s) of the spell.
Your case specifically
"I attack the orcs (plural) when I can see them"
Your trigger is being able to see more than one orc. And your action is to attack them. Assuming by "attack" you mean "attack with eldritch blast (which you DM probably understood, but you may want to rephrase it to be clearer), your wording is perfectly acceptable and would allow you to target multiple orcs with the spell if you wanted to. A clearer and technically more correct way to phrase it would be:
I will release eldritch blast when I see one or more orcs.
As long as you are careful with your wording there's no reason you can't target multiple, but it has nothing to do with your trigger condition.
Best Answer
The only thing the PHB has on the matter is on page 193-194;
Since it doesn't say anything about multiple targets, you could technically read it as you choose and roll attack/damage before you choose another one.
However, I'd say it's mostly up to you and the DM to choose, if it's faster or situationally beneficial to target and roll for one creature before targeting another or to choose all targets at once than go with whatever works.
On a side note though, Magic Missile specifically states
so I'd say you have to choose all targets first, at least for that.