There are a few different types of orbitals for example, s, p, d and f.
There is only one type of s orbital, s orbitals can hold a total of two electrons.
There are 3 types of p orbitals (each able to hold two electrons) so p orbitals hold a maximum of 6 electrons.
There are 5 types of d orbitals (each able to hold two electrons) so d orbitals can hold a maximum of 10 electrons.
Look at the periodic table and you will see the s, p, d and f sections, sometimes this helps visualise how the orbitals are filled.
So a 4s subshell will hold a maximum of two electrons. If this shell did contain two electrons then this means all of the shells "below" this one are also full (as they must fill in order):
1s2 2s2 2p6 3s2 3p6 4s2
This is the electronic configuration of Ca.
4s contains the valence electrons.
Note that Ca has 20 electrons.
It can also be written as [Ar] 4s2
as everything up to Ar is filled, so it is "easy" for Ca to lose the last two electrons (the valence electrons) to become Ca2+ which makes its electronic configuration the same as the noble gas Ar, which is quite stable (ie lower energy)
I hope this helps, let me know if it is too complicated (or not complicated enough).
Mike