Conceptually, they are different things. To see that, let's take a look at roughly what the equivalent Java would be. I'll use JVM for examples in this answer, but the same principles apply to all of the other Kotlin backends.
object Foo {
fun main() { ... }
}
This is roughly
class Foo {
public static void main() { ... }
}
Again, roughly. Technically, you'll get a singleton object and a method on it unless you use @JvmStatic (I assume there's some special handling for main that produces a static function on JVM, but I don't know that for a fact)
On the other hand,
object Foo {
val main: () -> Unit = { ... }
}
Here, we're declaring a property, which in Java is going to get implemented as a getter-setter pair
class Foo {
// Singleton instance
public static Foo instance = new Foo();
public Supplier<Void> main;
Foo() {
main = new Supplier<Void>() {
Void get() {
...
}
}
}
}
That is, there isn't actually a main method. There's a main field which, deep down somewhere, has a function inside of it. In my example above, that function is called get. In Kotlin, it's called invoke.
The way I like to think of it is this. Methods in Kotlin (i.e. the things you define on objects that designate their behavior) are not themselves first-class objects. They're second-class citizens which exist on an object. You can convert them to first-class objects by making them into functions. Functions are ordinary objects, like any other. If you take an ordinary object, which may or may not be a function, and call it with (), then you're actually invoking the method .invoke(...) on it. That is, () is an operator on objects which really ends up calling a method. So in Kotlin, functions are really just objects with a custom invoke and a lot of syntax sugar.
Your val defines a field which is a function. Your fun defines a method. Both of these can be called with (), but only one is a genuine method call; the other is secretly calling .invoke on another object. The fact that they look syntactically the same is irrelevant.
As the old adage goes, functions are a poor man's objects, and objects are a poor man's functions.