This paper provides a systematic study of fundamental combinatorial properties of one-dimensional, two-sided infinite simple Toeplitz subshifts. Explicit formulas for the complexity function, the palindrome complexity function and the repetitivity function are proven. Moreover, a complete description of the de Bruijn graphs of the subshifts is given. Finally, the Boshernitzan condition is characterised in terms of combinatorial quantities, based on a recent result of Liu and Qu. Particular simple characterisations are provided for simple Toeplitz subshifts that correspond to the orbital Schreier graphs of the family of Grigorchuk's groups, a class of subshifts that serves as main example throughout the paper.