In this case I think it also depends on the particular assembler. LDR Rd, =... is a pseudo instruction in at least the ARM and GNU assembler. The behaviour depends on what "Sample" is.
If "Sample" is an expression, e.g. a constant, then the value of Sample will be loaded. Sample might not even have an address if it is small enough.
If Sample is a symbol, e.g. a label, the assembler will load the address of Sample.
LDR r1, =SmallSample
# ---> this will assemble to "MOV r1, 5".
# ---> the assembler will generate a literal pool containing 0xdeadbeef and load from it using LDR r1, [pc,#offset]
Likewise if "Sample" is a function name, it'll load the address of the symbol
Sample .word 0xf00df00d
LDR r0, =Sample
#--> In this case the assembler will probably generate a literal pool containing the address of "Sample".