I tried this by listing all the matches for the world championship, the winner was (or champion if tied) listed first, the person who I believed had more experience in high level matches I bolded.
Steinitz-Zukertort 1886
Steinitz-Chigorin 1889
Steinitz-Gunsberg 1890
Steinitz-Chigorin 1892
Lasker-Steinitz 1894
Lasker-Steinitz 1896
Lasker-Marshall 1907
Lasker-Tarrasch 1908
Lasker-Schlechter 1910
Lasker-Janowsky 1910
Capablanca-Lasker 1921
Alekhine-Capablanca 1927
Alekhine-Bogoljubow 1929
Alekhine-Bogoljubow 1934
Euwe-Alekhine 1935
Alekhine-Euwe 1937
Botvinnik-Bronstein 1951
Botvinnik-Smyslov 1954
Smyslov-Botvinnik 1957
Botvinnik-Smyslov 1958
Tal-Botvinnik 1960
Botvinnik-Tal 1961
Petrosian-Botvinnik 1963
Petrosian-Spassky 1966
Spassky-Petrosian 1969
Fischer-Spassky 1972
Karpov-Korchnoi 1978
Karpov-Korchnoi 1981
Karpov-Kasparov 1984
Kasparov-Karpov 1985
Kasparov-Karpov 1986
Kasparov-Karpov 1987
Kasparov-Karpov 1990
Kasparov-Short 1993 (outside of FIDE)
Kasparov-Anand 1995
Kramnik-Kasparov 2000
Kramnik-Leko 2004
Kramnik-Topalov 2006
Anand-Kramnik 2008
Anand-Topalov 2010
Anand-Gelfand 2012
Experience wins 24-17
But then you count Lasker as the winner of the drawn match against Schlechter, Botvinnik as the winner of the drawn matches against Bronstein and Smyslov, Kramnik as the winner of the drawn match against Leko, and Karpov as winner of the aborted match against Kasparov. Kramnik vs Topalov and Anand vs Gelfand were decided in rapid chess, where Topalov and Gelfand are much weaker than Kramnik and Anand. Leko overperformed for a player that never was top three and never had played a match.
Of the last 16 finished matches the more experienced match player won in classical in four cases. One of them being Anand vs Kramnik, when not only Kramnik himself called Anand a typical tournament player that was supposed to be comparatively weak in matches. Anand vs Topalov was on the way to be drawn when Topalov avoided repetition in the last game not to have to play rapid tiebreak. I'd say that rapid chess strength and draw odds have been more important than match experience.
Yep. Carlsens da mudda fuggin chit. Oh, did I spell everything right?