As far as I know you'll have to apply for the visa in your home country, and will not be able to do it on the way. In theory. Whether or not you'll find an embassy that will be able to grant you a visa from a foreign country I don't know, but given the sheer number of countries you might be lucky.
Regarding the point of entry: due to the fact that you'll be getting a visa for one specific country that happens to be valid in all other Schengen countries as well you have to enter the Schengen area by way of the country that issued your visa. The Spanish immigration officers will have no clue how to deal with a Polish Schengen visa and vice versa. Once you're here there will be no passport checks whatsoever anymore - there are no borders between Schengen countries and if not for the small signs that welcome you in a different country, you might not even notice you've just passed from Spain to Portugal to France to Luxembourg to Germany to ......
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"Life is not a journey to the grave with the intention of arriving safely in one pretty and well preserved piece, but to skid across the line broadside, thoroughly used up, worn out, leaking oil, shouting GERONIMO!"
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