The zip file format is defined by PKWARE. You can find their file specification here.
Near the top you will find the header specification:
A. Local file header:
local file header signature 4 bytes (0x04034b50)
version needed to extract 2 bytes
general purpose bit flag 2 bytes
compression method 2 bytes
last mod file time 2 bytes
last mod file date 2 bytes
crc-32 4 bytes
compressed size 4 bytes
uncompressed size 4 bytes
file name length 2 bytes
extra field length 2 bytes
file name (variable size)
extra field (variable size)
From this you can see that the first 4 bytes of the header should be the file signature which should be the hex value 0x04034b50. Byte order in the file is the other way round - PKWARE specify that "All values are stored in little-endian byte order unless otherwise specified.", so if you use a hex editor to view the file you will see 50 4b 03 04 as the first 4 bytes.
You can use this to check if your file is a zip file. If you open the file in notepad, you will notice that the first two bytes (50 and 4b) are the ASCII characters PK.