Detailed spectroscopy of the neutron-deficient nucleus ^{36}Ca was obtained up to 9MeV using the ^{37}Ca(p,d)^{36}Ca and the ^{38}Ca(p,t)^{36}Ca transfer reactions. The radioactive nuclei, produced by the LISE spectrometer at GANIL, interacted with the protons of the liquid hydrogen target CRYPTA, to produce light ejectiles (the deuteron d or triton t) that were detected in the MUST2 detector array, in coincidence with the heavy residues identified by a zero-degree detection system. Our main findings are (i)a similar shift in energy for the 1_{1}^{+} and 2_{1}^{+} states by about -250 keV, as compared with the mirror nucleus ^{36}S; (ii)the discovery of an intruder 0_{2}^{+} state at 2.83(13)MeV, which appears below the first 2^{+} state, in contradiction with the situation in ^{36}S; and (iii)a tentative 0_{3}^{+} state at 4.83(17)MeV, proposed to exhibit a bubble structure with two neutron vacancies in the 2s_{1/2} orbit. The inversion between the 0_{2}^{+} and 2_{1}^{+} states is due to the large mirror energy difference (MED) of -516(130) keV for the former. This feature is reproduced by shell model calculations, using the sd-pf valence space, predicting an almost pure intruder nature for the 0_{2}^{+} state, with two protons (neutrons) being excited across the Z=20 magic closure in ^{36}Ca (^{36}S). This mirror system has the largest MEDs ever observed, if one excludes the few cases induced by the effect of the continuum.