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Ronaldo, 39, turned in a Nuno Mendes cross in the 34th minute of the match at the Estadio da Luz to reach the landmark.
Luka Modric gave Croatia a 55th-minute lead, moments after missing a penalty.
The All India Football Federation sacked Stimac following India's failure to reach the third round of the FIFA World Cup Qualifiers.
Klaus Gjasula scored a stoppage time goal to make it 2-2 in the Group B clash.
The Croats were no match for Spain's clever attacking play with coach Zlatko Dalic's game plans going out the window after about half an hour.
The Real Madrid and Croatia great had a video message for Indian captain Chhetri who will retire after the match against Kuwait on Thursday.
Standing 2.11m tall, Karlovic's huge serves and unorthodox style caused problems for some of the sport's biggest names and he won two of his three meetings with world No, 1 Novak Djokovic.
The final at the Feyenoord Stadium ended goalless after extra time, and defeat on penalties was a further heartbreak for an expectant Croatia.
Spain capitalised on a defensive lapse to take the lead inside three minutes as Yeremy Pino produced a cool finish
Donyell Malen handed the hosts a 34th-minute lead before Andrej Kramaric equalised from the penalty spot 10 minutes into the second half.
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