XPS/EDS vs FTIR/Raman
I think your main question is related to the difference? Have you heard a famous poem, The Blind Men and the Elephant? It is a story, I'd rather copy from Wikipedia

It is a story of a group of blind men who have never come across an elephant before and who learn and conceptualize what the elephant is like by touching it. Each blind man feels a different part of the elephant's body, but only one part, such as the side or the tusk. They then describe the elephant based on their limited experience and their descriptions of the elephant are different from each other. The moral of the parable is that humans have a tendency to claim absolute truth based on their limited, subjective experience as they ignore other people's limited, subjective experiences which may be equally true.


So replace these men with these analytical techniques and the sample with the elephant. XPS /EDS can see what Raman/FTIR cannot and vice versa.
XPS/EDS are elemental techniques and they will tell you what elements are present. Sometimes XPS spectrum, for an expert, can also reveal what is the oxidation state of that element, if you do high resolution scans. Each sample may take hours and hours.
Raman and FTIR can used to probe surfaces (they are fancy surface vibrational spectroscopy techniques) and it will tell you the molecular information, and even the angle at which the molecule is standing on the surface.
From the Raman spectra of an unknown it will be very hard to guess what elements are present.
In short, these are complementary techniques. Someone who is trying to study surfaces would use all of them - if needed.