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The layers of rock are known as "strata", and the study of their succession is known as "stratigraphy".
Fundamental to stratigraphy are a set of simple principles, based on elementary geometry, empirical observation of the way these rocks are deposited today, and gravity.
Geochronologists do not claim that radiometric dating is foolproof (no scientific method is), but it does work reliably for most samples.
The most common rocks observed in this form are sedimentary rocks (derived from what were formerly sediments), and extrusive igneous rocks (e.g., lavas, volcanic ash, and other formerly molten rocks extruded onto the Earth's surface).
Despite this, the "principle of cross cutting relationships" can be used to determine the sequence of deposition, folds, and faults based on their intersections -- if folds and faults deform or cut across the sedimentary layers and surfaces, then they obviously came after deposition of the sediments.
You can't deform a structure (e.g., bedding) that is not there yet!
As an example of how they are used, radiometric dates from geologically simple, fossiliferous Cretaceous rocks in western North America are compared to the geological time scale.
To get to that point, there is also a historical discussion and description of non-radiometric dating methods.
The simplest situation for a geologist is a "layer cake" succession of sedimentary or extrusive igneous rock units arranged in nearly horizontal layers.