The breather pipe for for the oil system is right below the oil cap on the mkiv golf. 'Mayo' on the cap and in the neck of the filler is commom. They are push fittings so pulling them off and cleaning them out is very easy. Disc brake cleaner does the job very well.
If the head gasket is leaking water into the oil then all the oil will be emulsified. Check the oil on the dip stick. If that's not emulsified then the head gasket hasn't gone.
Can't think what would produce a milky white fluid other than emulsified oil.
Your coolant should either be red or blue. Washer fluid is either green, blue or pink. A/C fluid would just evapourate. That's it for fluids.
Have you topped up the coolant recently? If you did, did you use the right type of coolant? VW have two and you can't mix them (according to VW).
As an alternative. Could it be a water leaking out, that is then mixing with oil/enigine grime/road salt before dripping on the floor?