LE stores bytes in the order you do most math operations on them (if you were to do it byte by byte and not in larger chunks, that is). Additions and subtractions proceed from least-significant bit (LSB) to most-significant bit (MSB), always, because that’s the order carries (and borrows) are generated. Multiplications form partial products from smaller terms (at the limit, individual bits, though for hardware you’re more likely to use radix-4 booth recoding or similar) and add them, and the final addition likewise is LSB to MSB. Long division is the exception and works its way downwards from the most significant bits, but divisions are generally much less frequent than additions, subtractions and multiplication.

Arbitrary-precision arithmetic (“bignum arithmetic”) thus typically chops up numbers into segments (“legs”) matching the word size of the underlying machine, and stores these words in memory ordered from least significant to most significant – on both LE and BE architectures.

All 8-bit ISAs I’m personally familiar with (Intel 8080, Zilog Z80, MOS 6502) use LE, presumably for that reason; it’s the more natural byte order for 16-bit numbers if you only have an 8-bit ALU. (That said, Motorola’s 8-bit 6800 apparently used BE). And consequently, if you’re designing a new architecture with the explicit goal of being source-code compatible with the 8080 (yes, x86 was already constrained by backwards-compatibility considerations even for the original 8086!) it’s going to be little-endian.